Solid-state imaging device, method of manufacturing the same, and electronic apparatus

ABSTRACT

A solid state imaging device that includes a substrate having oppositely facing first and second surfaces and a photoelectric conversion unit layer having a light incident side facing away from the substrate. The substrate includes a first photoelectric conversion unit and a second photoelectric conversion and the photoelectric conversion layer includes a third photoelectric conversion unit.

RELATED APPLICATION DATA

This application is a continuation-in-part of U.S. patent applicationSer. No. 12/836,741 filed Jul. 15, 2010 the entirety of which isincorporated herein by reference to the extent permitted by law. Thepresent invention claims priority to Japanese Patent Application No. JP2009-172383 filed in the Japanese Patent Office on Jul. 23, 2009 theentirety of which also is incorporated by reference herein to the extentpermitted by law.

BACKGROUND OF THE INVENTION

The present invention relates to a solid-state imaging device, a methodof manufacturing the same, and an electronic apparatus.

Solid-state imaging devices are broadly classified into tworepresentative kinds of solid-state imaging devices of a CCD (ChargeCoupled Device) image sensor and a CMOS (Complementary Metal OxideSemiconductor) image sensor. In recent years, the size of a pixel hasdecreased and the number of photons incident on a unit pixel hasdecreased in CCD image sensors and CMOS image sensors. As a result,sensitivity deteriorates the solid-state image sensor and there is adecrease in the signal to noise ratio (S/N).

In widely used pixel arrangements where red, green, and blue pixels arearranged on planar surface, such as the Bayer arrangement that usesprimary color filters, green and blue light does not penetrate the colorfilter in red pixels and is not used in photoelectric conversion.Therefore, sensitivity of the image sensor may decrease. Moreover, whena color signal is formed by executing an interpolation process betweenpixels, false color may arise.

In order to solve these problems, Japanese Unexamined PatentApplication. Publication No. 2007-12796 discloses a solid-state imagingdevice in which green, blue, and red photoelectric conversion units arelaminated in a depth direction in the same pixel. In this solid-stateimaging device, a blue photodiode (photoelectric conversion unit) and ared photodiode (photoelectric conversion unit) are formed in the depthdirection in a silicon substrate. In addition, the solid-state imagingdevice includes an organic photoelectric conversion unit in which agreen organic photoelectric conversion layer is interposed betweenelectrodes and formed on the upper layer of the front surface of thesilicon substrate on the side of a light-sensing portion with a wiringlayer interposed between the photoelectric conversion layer and thesubstrate. According to the configuration disclosed in JapaneseUnexamined Patent Application Publication No. 2007-12796 light loss doesnot occur in the color filter and the sensitivity of the solid-stateimaging device is improved. Moreover, since the interpolation process isnot performed between pixels, false color does not occur.

Japanese Unexamined Patent Application Publication No. 2008-258474discloses a back-illuminated CMOS image sensor including color filters,a photoelectric conversion unit with photodiodes laminated in a depthdirection, and an organic photoelectric conversion layer. Thesolid-state imaging device disclosed in Japanese Unexamined PatentApplication Publication No. 2008-258474 includes color filters arrangedin a yellow and cyan check pattern. The photoelectric conversion unitformed by red and blue photodiodes is disposed in a manner thatcoordinates with the yellow and cyan filters. Moreover, an organicphotoelectric conversion unit is disposed in the upper layer f eachphotodiode. In this solid-state imaging device, the organicphotoelectric conversion unit is sensitive to green light, thephotodiode of the yellow filter is sensitive to red light, and thephotodiode of the cyan filter is sensitive to blue light.

SUMMARY OF THE INVENTION

In an organic and inorganic hybrid type photoelectric conversion unit,as disclosed in Japanese Unexamined. Patent Application Publication No.2007-12796 the wiring layer is interposed between the Si photodiodeexecuting the photoelectric conversion and the organic photoelectricconversion unit on the upper layer. In this structure, the distancebetween the photodiodes and the organic photoelectric conversion unit islarge. In solid-state imaging devices with this configuration, when an Fnumber of a camera lens is changed, the influence of indirect light issmall and the variation in sensitivity is small in the organicphotoelectric conversion unit that is close to the on-chip lens.However, the variation in sensitivity may be large in photoelectricconversion units of the Si photodiode that are, further from the on-chiplens and receives more indirect light. That is, when the configurationhaving the organic and inorganic hybrid type photoelectric conversionunit is used, spectral balance between colors may be varied inaccordance with the F number. For this reason, when a linear matrixprocess synchronized with mechanical control of the F number is notexecuted, the color may be changed in each optical zoom factor. Themechanical control may be executed in principle. However, when a digitalsignal process (DSP) is executed to execute signal processing insynchronization with the lens control, cost may be increased. Therefore,application to a general DSP or the like is not practical.

It is desirable to provide a solid-state imaging device capable ofsuppressing the variation in sensitivity between colors by suppressingdependence on the F number of each color in a configuration of anorganic and inorganic hybrid type photoelectric conversion unit, and amethod of manufacturing the solid-state imaging device.

It is desirable to provide an electronic apparatus, such as a camera,including the solid-state imaging device.

According to an embodiment of the invention, a solid state imagingdevice includes a substrate having oppositely facing first and secondsurfaces, a photoelectric conversion unit layer having a light incidentside facing away from the substrate, a first photoelectric conversionunit and a second photoelectric conversion within the substrate and athird photoelectric conversion unit within the photoelectric conversionunit layer.

According to an embodiment of the invention, the solid state imagingdevice includes a multi-wiring layer outside of the substrate andlocated in a layer carried on the second substrate surface.

According to an embodiment of the invention the first and secondphotoelectric conversion units are an inorganic photoelectric conversionmaterial and the third photoelectric conversion unit is an organicphotoelectric conversion material.

According to an embodiment of the invention, the substrate has a firstsubstrate surface that faces the light incident side and a secondsubstrate surface that faces away from the incident light surface. Inthis embodiment, the first photoelectric conversion unit is between thefirst substrate surface and the second photoelectric conversion unit andthe second photoelectric conversion unit is between the firstphotoelectric conversion unit and the second substrate surface.

According to an embodiment of the invention, the first photoelectricconversion unit is particularly sensitive to blue light, the secondphotoelectric conversion unit is particularly sensitive to red light andthe third photoelectric conversion unit is particularly sensitive togreen light.

According to an embodiment of the invention, the third photoelectricconversion unit further comprises a photoelectric conversion materiallayer, an upper electrode on a surface of the photoelectric conversionmaterial layer facing the light incident side and a lower electrode on asurface of the photoelectric conversion material layer facing thesubstrate. In this embodiment, a signal charge in the thirdphotoelectric conversion unit is transferred therefrom via the lowerelectrode.

According to an embodiment of the invention, a first insulating layer Ilocated on each edge of the third photoelectric conversion materiallayer.

According to an embodiment of the invention a charge accumulation layeris located within the substrate adjacent to the second substratesurface.

According to an embodiment of the invention, the solid state imagingdevice includes an insulating layer made of HfO₂ and biased with a fixednegative voltage. In this embodiment, the insulating layer is betweenthe photoelectric conversion unit layer and the substrate.

According to an embodiment of the invention, the solid state imagingdevice includes a thin film transistor within the photoelectricconversion unit layer.

According to an embodiment of the invention, a solid state imagingdevice includes a plurality of pixels arranged in a matrix having rowsand columns. In this embodiment, each pixel comprises at least a portionof a substrate having oppositely facing first and second substratesurfaces, a photoelectric conversion unit layer having a light incidentside facing away from the substrate, a first photoelectric conversionunit and a second photoelectric conversion within the at least a portionof a substrate and a third photoelectric conversion unit withinphotoelectric conversion unit layer.

According to an embodiment of the invention, each pixel includes a thinfilm transistor within the photoelectric conversion unit layer. In thisembodiment, the drain regions of the thin film transistors arrangedalong a common vertical line are commonly connected via a common wire.

According to an embodiment of the invention, there is a method formanufacturing a solid state imaging device that includes forming asubstrate that has oppositely facing first and second surfaces andforming a first photoelectric conversion unit and a second photoelectricconversion within the substrate. This method also includes forming aphotoelectric conversion unit layer, including a third photoelectricconversion unit therein. The photoelectric conversion unit layer has alight incident side facing away from the substrate.

According to an embodiment of the invention, there is an electronicdevice that includes a solid state imaging device. In this embodiment,the solid state imaging device includes a substrate having oppositelyfacing first and second surfaces and a photoelectric conversion unitlayer having a light incident side facing away from the substrate. Inthis embodiment, a first photoelectric conversion unit and a secondphotoelectric conversion are located within the substrate and a thirdphotoelectric conversion unit is within the photoelectric conversionunit layer. Furthermore, in this embodiment the electronic device has animaging function.

In the solid-state imaging device according to the embodiments of theinvention, since the inorganic photoelectric conversion unit isconfigured so as to be close to the organic photoelectric conversionunit, it is possible to suppress the dependence on the F number of eachcolor. Therefore, it is possible to suppress the variation in thesensitivity between colors.

In the method of manufacturing the solid-state imaging device accordingto the embodiments of the invention, since the inorganic photoelectricconversion unit is configured so as to be close to the organicphotoelectric conversion unit, it is possible to suppress the dependenceon the F number of each color. Accordingly, the solid-state imagingdevice capable of suppressing the variation in the sensitivity betweencolors can be manufactured.

The electronic apparatus according to the embodiment of the inventionincludes the back-illuminated solid-state imaging device in which theinorganic photoelectric conversion unit is configured so as to be closeto the organic photoelectric conversion unit in the same pixel.Therefore, it is possible to suppress the dependence on the F number ofeach color and suppress the variation in the sensitivity between colors.Accordingly, the electronic apparatus with high quality can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagram illustrating the configuration of major units of asolid-state imaging device according to a first embodiment of theinvention.

FIG. 2 is a sectional view illustrating the major units of a solid-stateimaging device according to the first embodiment.

FIG. 3 is a sectional view illustrating transmission transistors Tr12and Tr13 according to the first embodiment.

FIG. 4 is a sectional view illustrating a transmission transistor Tr11according to the first embodiment.

FIG. 5 is a schematic sectional view illustrating a driving operationaccording to the first embodiment.

FIG. 6 is a diagram illustrating a process of manufacturing thesolid-state imaging device according to the first embodiment.

FIG. 7 is a diagram illustrating a process of manufacturing thesolid-state imaging device according to the first embodiment.

FIG. 8 is a diagram illustrating a process of manufacturing thesolid-state imaging device according to the first embodiment.

FIG. 9 is a diagram illustrating a process of manufacturing thesolid-state imaging device according to the first embodiment.

FIG. 10 is a diagram illustrating a process of manufacturing thesolid-state imaging device according to the first embodiment.

FIG. 11 is a diagram illustrating a process of manufacturing thesolid-state imaging device according to the first embodiment.

FIG. 12 is a diagram illustrating a process of manufacturing thesolid-state imaging device according to the first embodiment.

FIG. 13 is a diagram illustrating a process of manufacturing thesolid-state imaging device according to the first embodiment.

FIG. 14 is a diagram illustrating a process of manufacturing thesolid-state imaging device according to the first embodiment.

FIG. 15 is a diagram illustrating a process of manufacturing thesolid-state imaging device according to the first embodiment.

FIG. 16 is a diagram illustrating a process of manufacturing thesolid-state imaging device according to the first embodiment.

FIG. 17 is a diagram illustrating a process of manufacturing thesolid-state imaging device according to the first embodiment.

FIG. 18 is a diagram illustrating the configuration of major units of asolid-state imaging device according to a second embodiment of theinvention.

FIG. 19 is a diagram illustrating a process of manufacturing thesolid-state imaging device according to the second embodiment.

FIG. 20 is a diagram illustrating a process of manufacturing thesolid-state imaging device according to the second embodiment.

FIG. 21 is a diagram illustrating a process of manufacturing thesolid-state imaging device according to the second embodiment.

FIG. 22 is a diagram illustrating a process of manufacturing thesolid-state imaging device according to the second embodiment.

FIG. 23 is a diagram illustrating a process of manufacturing thesolid-state imaging device according to the second embodiment.

FIG. 24 is a diagram illustrating a process of manufacturing thesolid-state imaging device according to the second embodiment.

FIG. 25 is a diagram illustrating a process of manufacturing thesolid-state imaging device according to the second embodiment.

FIG. 26 is a diagram illustrating a process of manufacturing thesolid-state imaging device according to the second embodiment.

FIG. 27 is a diagram illustrating a process of manufacturing thesolid-state imaging device according to the second embodiment.

FIG. 28 is a diagram illustrating a process of manufacturing thesolid-state imaging device according to the second embodiment.

FIG. 29 is a diagram illustrating a process of manufacturing thesolid-state imaging device according to the second embodiment.

FIG. 30 is a diagram illustrating the configuration of major units of asolid-state imaging device according to a third embodiment of theinvention.

FIG. 31 is a sectional view illustrating transmission transistors. Tr12and Tr13 according to the third embodiment.

FIG. 32 is a sectional view illustrating a transmission transistor Tr11according to the third embodiment.

FIG. 33 is a diagram illustrating the configuration of major units of asolid-state, imaging device, according to a fourth embodiment of theinvention.

FIG. 34 is a diagram illustrating the configuration of major units of asolid-state imaging device according to a fifth embodiment of theinvention.

FIG. 35 is a diagram illustrating the configuration of major units of asolid-state imaging device according to a sixth embodiment of theinvention.

FIG. 36 is a diagram illustrating a process of manufacturing thesolid-state imaging device according to the sixth embodiment.

FIG. 37 is a diagram illustrating a process of manufacturing thesolid-state imaging device according to the sixth embodiment.

FIG. 38 is a diagram illustrating a process of manufacturing thesolid-state imaging device according to the sixth embodiment.

FIG. 39 is a diagram illustrating a process of manufacturing thesolid-state imaging device, according to the sixth embodiment.

FIG. 40 is a diagram illustrating a process of manufacturing thesolid-state imaging device according to the sixth embodiment.

FIG. 41 is a diagram illustrating a process of manufacturing thesolid-state imaging device according to the sixth embodiment.

FIG. 42 is a diagram illustrating a process of manufacturing thesolid-state imaging device according to the sixth embodiment.

FIG. 43 is a diagram illustrating a process of manufacturing thesolid-state imaging device according to the sixth embodiment.

FIG. 44 is a diagram illustrating a process of manufacturing thesolid-state imaging device according to the sixth embodiment.

FIG. 45 is a diagram illustrating a process of manufacturing thesolid-state imaging device according to the sixth embodiment.

FIG. 46 is a diagram illustrating the configuration of major units of asolid-state imaging device according to a seventh embodiment of theinvention.

FIG. 47 is a diagram illustrating the circuit configuration of majorunits according to the seventh embodiment.

FIG. 48 is a schematic diagram illustrating the configuration of majorunits of a solid-state imaging device according to an eighth embodimentof the invention.

FIG. 49 is a schematic sectional view illustrating the solid-stateimaging device in FIG. 44 .

FIG. 50 is a schematic sectional view illustrating a transmissiontransistor of the solid-state imaging device according to a modifiedexample of the sixth embodiment.

FIG. 51 is a schematic diagram illustrating the configuration of a CMOSsolid-state imaging device.

FIG. 52 is a schematic diagram illustrating the configuration of anelectronic apparatus according to an embodiment of the invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Hereinafter, preferred embodiments (hereinafter, referred to asembodiments) of the invention will described. The description will bemade in the following order.

1. Configuration of CMOS Solid-State Imaging Device 2. First Embodiment(Configuration of Solid-State Imaging Device and Method of Manufacturingthe Same) 3. Second Embodiment (Configuration of Solid-State ImagingDevice and Method of Manufacturing the Same) 4. Third Embodiment(Configuration of Solid-State Imaging Device) 5. Fourth Embodiment(Configuration of Solid-State Imaging Device) 6. Fifth Embodiment(Configuration of Solid-State Imaging Device) 7. Sixth Embodiment(Configuration of Solid-State Imaging Device and Method of Manufacturingthe Same) 8. Seventh Embodiment (Configuration of Solid-State ImagingDevice) 9. Eighth Embodiment (Configuration of Solid-State ImagingDevice) 10. Ninth Embodiment (Configuration of Electronic Apparatus) 1.Exemplary Overall Configuration of CMOS Solid-State Imaging Device

FIG. 51 is a diagram illustrating an exemplary overall configuration ofa CMOS solid-state imaging device according to each embodiment of theinvention. As shown in FIG. 51 , a solid-state imaging device 1according to the embodiments includes a pixel section-called an imagingarea) 3, where plural pixels 2 including a photoelectric conversion unitare regularly arranged two-dimensionally in a semiconductor substrate 11such as a silicon substrate, and a peripheral circuit section. The pixel2 includes the photoelectric conversion unit and plural pixeltransistors (so-called MOS transistors). For example, the plural pixeltransistors include three transistors such as a transmission transistor,a reset transistor and an amplification transistor. Alternatively, theplural pixel transistors may include four transistors in addition to aselection transistor. Since an equivalent circuit of a unit pixel is thesame as a general equivalent circuit, the detailed description isomitted. A so-called pixel shared structure may be applied in which theplural photoelectric conversion units share the other pixel transistorsexcept for the transmission transistor and share the floating diffusionin the pixel.

The peripheral circuit section includes a vertical driving circuit 4,column signal processing circuits 5, a horizontal driving circuit 6, anoutput circuit 7, and a control circuit 8.

The control circuit 8 receives data instructing an input clock, anoperation mode, or the like, and outputs data such as internalinformation regarding the solid-state imaging device. That is, thecontrol circuit 8 generates a clock signal or a control signal servingas a reference signal of the operations of the vertical driving circuit4, the column signal processing circuits 5, the horizontal drivingcircuit 6, and the like in accordance with a vertical synchronoussignal, a horizontal synchronous signal, and a master clock. Thesesignals are input to the vertical driving circuit 4, the column signalprocessing circuits 5, the horizontal driving circuit 6, and the like.

The vertical driving circuit 4, which includes a shift register, forexample, selects pixel driving wires, supplies pulses to drive pixels tothe selected pixel driving wires, and drives the pixels in a row unit.That is, the vertical driving circuit. 4 selectively scans the pixels 2of the pixel section 3 sequentially in a row unit in a verticaldirection and supplies the column signal processing circuits 5, via thevertical signal lines 9, with pixel signals corresponding to signalcharges generated in accordance with an amount of light received in thephotodiodes, for example, serving as the photoelectric conversionelement of each pixel 2.

The column signal processing circuit 5 is disposed in each column of thepixels 2, for example. The column signal processing circuit 5 executes asignal processing operation, such as a noise removing operation, onsignals output from the one-row pixels 2 in each pixel column. That is,the column signal processing circuit 5 executes a signal processingoperation such as a CDS operation of removing a fixed pattern noisepresent in the pixel 2, a signal amplifying operation, or an ADconverting operation. Horizontal selection switches (not shown) aredisposed and connected between the output terminals of the column signalprocessing circuits 5 and the horizontal signal line 10.

The horizontal driving circuit 6 includes a shift register, for example.The horizontal driving circuit 6 sequentially outputs horizontalscanning pulses and sequentially selects the column signal processingcircuits 5 to output the pixel signals from the column signal processingcircuits 5 to the horizontal signal line 10.

The output circuit 7 executes a signal processing operation on thesignals sequentially supplied from the column signal processing circuits5 via the horizontal signal line 10 and outputs the signals. Forexample, the output circuit 7 executes only a buffering operation orexecutes a black-level adjusting operation, a column variationadjustment operation, and various digital signal processing operationsinput/output terminals 12 exchange signals with an external device.

2. First Embodiment Configuration of Solid-State Imaging Device

FIG. 1 is a diagram illustrating a solid-state imaging device accordingto a first embodiment of the invention. The solid-state imaging deviceaccording to this embodiment is a CMOS solid-state imaging device. FIG.1 is a sectional view illustrating one pixel 20 in the pixel section ofthe CMOS solid-state imaging device.

A solid-state imaging device 21 according to the first embodimentincludes three photoelectric conversion units. The first and secondphotoelectric conversion units PD1 and PD2 are within a substrate 22.The substrate has a front surface, also called a second substratesurface (24) and a rear surface, also called a first substrate, surface(23). The third photoelectric conversion unit 39 is within aphotoelectric conversion layer 61. The photoelectric conversion layer 61has an incident light side 61 a. In this embodiment, the thirdphotoelectric conversion unit 39 can be an inorganic photoelectric unitand the first and second photoelectric conversion units PD1 and PD2 canbe inorganic and have a pn junction. Further, the organic photoelectricconversion unit 39 and the inorganic photoelectric conversion units PD1and PD2 are laminated in the same pixel; in a depth direction, that is,PD1 is between the first substrate, surface and PD2 and PD2 is betweenPD1 and the second substrate surface.

More specifically, the solid-state imaging device 21 includes asemiconductor substrate (silicon substrate) 22 in which an inorganicphotoelectric conversion unit, which is described below, is formed. Alight-sensing portion on which light is incident is formed on a rearsurface 23 of the substrate 22. The rear surface 23 can also be referredto as a first substrate surface. A circuit including so-called readingcircuit is formed on a front surface 24 of the substrate 22. The frontsurface 24 can also be referred to as a second substrate surface. Thatis, the solid-state imaging device 21 include a light-sensing portion 25formed on the rear surface 23 of the substrate 22 and a circuitformation surface 26 formed on the front surface 24 opposite, to thelight-sensing portion 25. The semiconductor substrate 22 is configuredas a first type semiconductor substrate, for example, an n-typesemiconductor substrate.

In the semiconductor 22, the two inorganic photoelectric conversionunits having the pn junction, that is, a first photodiode PD1 and asecond photodiode PD2 are laminated from the rear surface 23 in thedepth direction. In the semiconductor substrate 22, a p-typesemiconductor region 28 serving as a hole accumulation layer, an n-typesemiconductor region 29 serving as a charge accumulation layer, and ap-type semiconductor region 31, an n-type semiconductor region 32serving as a charge accumulation layer, and a p-type semiconductorregion 33 are formed from the rear surface 23 in the depth direction.The first photodiode PD1 is formed to use the n-type semiconductorregion 29 as a charge accumulation layer. The second photodiode PD2 isformed to use the n-type semiconductor region 32 as a chargeaccumulation layer.

In this embodiment, the first photodiode PD1 is a photodiode that isparticularly sensitive to blue light and the second photodiode PD2 is aphotodiode that is particularly sensitive to red light. A part of eachof the n-type semiconductor regions 29 and 32 extends to the frontsurface 24 of the substrate 22. Extension portions 29 a and 32 a extendfrom the opposite, ends of the n-type semiconductor regions 29 and 32,respectively. The p-type semiconductor region 28 serving as a holeaccumulation layer is connected to a p-type semiconductor well region onthe front surface. A p-type semiconductor region serving as a holeaccumulation layer is formed in each interface between an insulatinglayer facing the front surface 24 of the substrate and the n-typesemiconductor region 29 of the first photodiode PD1 and the n-typesemiconductor region 32 of the second photodiode PD2.

A first color organic photoelectric conversion unit 39, aka, the thirdphotoelectric conversion unit, in which an upper electrode 37 and alower electrode 38 a are formed on both upper and lower surfaces of anorganic photoelectric conversion layer 36, is laminated on the upperlayer of the rear surface of the substrate in the region where the firstphotodiode PD1 and the second photodiode PD2 are formed with aninsulating layer 34 interposed therebetween. In this embodiment, theorganic photoelectric conversion unit 39 is particularly sensitive togreen light. The upper electrode 37 and the lower electrode 38 a areformed of a transparent conductive layer such as an indium tin oxide(ITO) layer or an indium zinc oxide layer.

In this embodiment, the organic photoelectric conversion unit 39 is aunit for a green color, the first photodiode PD1 is a photodiode for ablue color, and the second photodiode PD2 is a photodiode for a redcolor or a combination except for the red color. However, another colorcombination is possible. For example, the organic photoelectricconversion unit 39 may be a unit for a red color or a blue color, andthe first photodiode PD1 and the second photodiode PD2 may bephotodiodes for other colors. In this case, the positions of the firstphotodiode PD1 and the second photodiode PD2 in the depth direction aredetermined in accordance with the colors.

The organic photoelectric conversion layer executing photoelectricconversion into light with a green wavelength may be formed of anorganic photoelectric conversion material such as a rhodamine-basedpigment, a merocyanine-based pigment, or a quinacridone-based pigment.The organic photoelectric conversion layer executing photoelectricconversion into light with a red wavelength may be formed of an organicphotoelectric conversion material such as a phthalocyanine-basedpigment. The organic photoelectric conversion layer executingphotoelectric conversion into light with a blue wavelength may be formedof an organic photoelectric conversion material such as a coumarin-basedpigment, tris-8-hydroxyquinolines Al(Alq3), or a merocyanine-basedpigment.

In the organic photoelectric conversion unit 39, transparent lowerelectrodes 38 a and 38 b halved on the insulating layer 34 are formedand an insulating layer 41 is formed to isolate both the lowerelectrodes 38 a and 38 b from each other. The organic photoelectricconversion layer 36 on the lower electrode 38 a and the transparentupper electrode 37 on the organic photoelectric conversion layer 36 areformed. An insulating layer 42 is formed to protect the end surfaces ofthe patterned upper electrode 37 and the patterned organic photoelectricconversion layer 36, that is, the end surfaces patterned by etching. Inthis state, the upper electrode 37 is connected to the other lowerelectrode 38 b via a contact metal layer 43 by another conductive layer.

By forming the protective insulating layer, it is possible to protectthe end surface of the organic photoelectric conversion layer, and thusto prevent the organic photoelectric conversion layer and the electrodesfrom coming into contact with each other. The material of the upperelectrode 37 is selected in consideration of a work function. Therefore,when another electrode material comes into contact with the end surfaceof the organic photoelectric conversion layer, that is, the side wallthereof, a dark current may occur in the side wall of the organicphotoelectric conversion layer. Since the organic photoelectricconversion layer 36 and the upper electrode 37 are consistently formed,the clean interface therebetween is formed. However, the side, wall ofthe organic photoelectric conversion layer 36 patterned by dry etchingor the like is not clean. Moreover, when another electrode materialcomes into contact with the side wall thereof, the interface maydeteriorate, and thus a dark current may increase.

In the semiconductor substrate 22 in one pixel 20, a pair of conductiveplugs 45 and 46 formed through the semiconductor substrate 22 is formed.The lower electrode 38 a of the organic photoelectric conversion unit 39is connected to the conductive plug 45, and the lower electrode 38 bconnected to the upper electrode 37 is connected to the other conductiveplug 46. Since one conductive plug 45 may exist f r the lower electrode,at least one conductive plug may exist across the pixel region, as longas the upper electrode is not isolated in each pixel.

In order to prevent short-circuit with Si, for example, the conductiveplugs 45 and 46 may be formed of SiO₂, a W plug having a SiN insulatinglayer circumferentially, or a semiconductor layer formed byion-implanting. In this embodiment, electrons are used as signalcharges. Therefore, the conductive plug 45 is an n-type semiconductorlayer, when the conductive plug 45 is formed in the semiconductor layerby ion-implanting. It is desirable that the upper electrode is of ap-type, since holes are extracted.

In this embodiment, in order to accumulate electrons, which serve as thesignal charges in the pairs of electrons and holes subjected tophotoelectric conversion by the organic photoelectric conversion unit39, via the upper electrode 37 and the conductive plugs, an n-typesemiconductor region 47 for charge accumulation is formed on the surfaceof the substrate 22.

It is desirable to use a layer with negative fixed charges as theinsulating layer 34 on the rear surface 23 of the semiconductorsubstrate 22. It is desirable to use a hafnium oxide layer 342 as thelayer with negative fixed charges, for example, as shown in FIG. 2 .That is, the insulating layer 34 has a three-layer structure in which asilicon oxide layer 341, the hafnium oxide layer 342, a silicon oxidelayer 343 are laminated sequentially from the rear surface 23. Since thehafnium oxide layer 342 has the negative fixed charges, as describedbelow, a hole accumulation state of the interface between the silicon ofthe p-type semiconductor region (silicon) 28 and the insulating layer 34is enhanced. Therefore, it is advantageous to prevent the dark currentfrom occurring.

The plural pixel transistors corresponding to the organic photoelectricconversion unit 39, the first photodiode PD1 and the second photodiodePD2 are formed on the circuit formation surface 26 on the side of thefront surface of the substrate 22. The plural pixel transistors may havethe above-described four-transistor configuration or three-transistorconfiguration. Alternatively, the above-described configuration sharinga pixel transistor may be applied. In FIGS. 3 and 4 illustrating thecross-section different from the cross-section in FIG. 1 , the pixeltransistor is schematically illustrated. FIGS. 3 and 4 representativelyshow the transmission transistor of the plural pixel transistors. Thatis, in the organic photoelectric conversion unit 39, as shown in FIG. 4, the n-type semiconductor region 47 for charge accumulation isconnected to a transmission transistor Tr11 including an n-typesemiconductor region 48 serving as a floating diffusion unit and atransmission gate electrode 49. In the first photodiode PD1 as shown inFIG. 3 , the extension portion 29 a of the n-type semiconductor region29 serving as a charge accumulation layer is connected to a transmissiontransistor Tr12 including an n-type semiconductor region 51 serving as afloating diffusion unit and a transmission gate electrode 52. In thesecond photodiode PD2 as shown in FIG. 3 , the extension portion 32 a ofthe n-type semiconductor region 32 serving as a charge accumulationlayer is connected to a transmission transistor Tr13 including an n-typesemiconductor region 53 serving as a floating diffusion unit and atransmission gate electrode 54.

Even though the arrangement positions are different, the transmissiontransistors Tr11 to Tr13 in FIGS. 3 and 4 are illustrated as gateelectrodes 49, 52, and 54 in FIG. 1 for convenience. The same is appliedto the following embodiments.

At least, a p-type semiconductor region 50 serving as a holeaccumulation layer is formed in the interface with the insulating layer,which faces the front surface 24 of the substrate of the n-typesemiconductor regions 29 a and 32 a respectively forming the firstphotodiode PD1 and the second photodiode PD2. In FIG. 3 , the p-typesemiconductor region serving as the hole accumulation layer is formed soas to include, the interface between the p-type semiconductor region 33and the insulating layer. The p-type semiconductor region 50 serving asthe hole accumulation layer is formed in the interface with theinsulating layer, which faces the front surface 24 of the substrate ofthe re-type semiconductor region 47 for charge accumulation in theorganic photoelectric conversion unit 39. The pixel transistor includingthe transmission transistors Tr11 to Tr1.3 is formed in the p-typesemiconductor well region on the front surface of the substrate.

Although not illustrated, the pixel transistors of the pixel section areformed on the front surface of the semiconductor substrate 22 and aperipheral circuit such as a logic circuit is formed in the peripheralcircuit section.

A multi-layer wiring layer 58, in which layer wirings 57 of plurallayers are disposed with an inter-layer insulating layer 56 interposedtherebetween, is formed on the front surface of the semiconductorsubstrate 22. A supporting substrate 59 is joined to the multi-layerwiring layer 58.

The rear surface of the semiconductor substrate 22, more specifically,the surface of the upper electrode 37 of the organic photoelectricconversion unit 35 serves as the light-sensing portion 25. An on-chiplens 62 is formed on the organic photoelectric conversion unit 39 with aplanarization layer 61 interposed therebetween. In this embodiment, nocolor filter is formed.

An operation (driving method) of the solid-state imaging device 21according to the first embodiment will be described. The solid-stateimaging device 21 is configured as a so-called back-illuminatedsolid-state imaging device emitting light from the rear surface of thesubstrate. In this embodiment, a negative fixed voltage VL (<0 V) isapplied to the lower electrode 38 a of the organic photoelectricconversion unit 39 via the necessary wiring 57 of the multi-layer wiringlayer 58, and a voltage VU (<VL), such as a power voltage, higher thanthe voltage VL of the lower electrode 38 a is applied to the upperelectrode 37 at the time of accumulating the charges. That is, anegative voltage VL is applied to the lower electrode 38 a close to thesemiconductor substrate 22. The voltage of 0 V is applied from thenecessary wiring 57 to the p-type semiconductor region 28 serving as thehole accumulation layer via the extension portion 28 a.

The application of a high voltage VH to the upper electrode 37 at thetime of accumulating the charges will be described with reference toFIG. 5 . FIG. 5 is a schematic diagram illustrating the organicphotoelectric conversion unit 39. At the time of reset, the resettransistor Tr2 and the transmission transistor Tr11 are turned on, andthe n-type semiconductor region 48 serving as a floating diffusion unit(FD) and the n-type semiconductor region 47 for charge accumulation arereset by a power voltage VDD. Thereafter, when the reset transistor Tr2and the transmission transistor Tr11 are turned off to accumulatecharges, the potential of the n-type semiconductor region 47 and theupper electrode 37 connected to the n-type semiconductor region 47 arevaried in accordance with the accumulated charges. The potential becomesa signal potential.

When light is incident on one pixel 20 without passing through a colorfilter at the time of accumulating the charges, green-wavelength lightis subjected to photoelectric conversion by the organic photoelectricconversion layer 36 capable of absorbing the green-wavelength light. Ofthe pairs of the electrons and holes generated by the photoelectricconversion, the electrons serving as the signal charges are guided tothe upper electrode 37 with the high voltage VU and are accumulated inthe n-type semiconductor region 47 via the conductive plug 46. The holessubjected to the photoelectric conversion are guided to the lowerelectrode 38 a with the potential VL and are discharged via theconductive plug 45 and the necessary wiring 57. The blue-wavelengthlight is absorbed and subjected to photoelectric conversion by the firstphotodiode PD1 formed in a shallow portion close to the rear surface, ofthe semiconductor substrate 22, and the signal charges corresponding tothe blue color are accumulated in the n-type semiconductor region 29.The red-wavelength light is absorbed and subjected to photoelectricconversion by the second photodiode PD2 formed in a deep portion fromthe rear surface of the semiconductor substrate 22, and the signalcharges corresponding to the red color are accumulated in the n-typesemiconductor region 32.

At the time of reading the charges, the transmission transistors. Tr11,Tr12, and Tr13 are turned on. When the transmission transistors areturned on, the accumulated signal charges (electrons) of the organicphotoelectric conversion unit 39, the first photodiode PD1 and thesecond photodiode PD2 are transmitted to the floating diffusion units(FD) 48, 51, and 54, respectively. The pixels signals of the red, green,and blue colors are read and output by the vertical signal lines via theother pixel transistors.

In the solid-state imaging device 21 according to the first embodiment,the organic photoelectric conversion unit 39, the first photodiode PD1and the second photodiode PD2 of a back-illuminated type are laminatedin the depth direction. With such a configuration, the first photodiodePD1 and the organic photoelectric conversion unit 39 are close to eachother. That is, since the multi-layer wiring layer 58 does not existbetween the first photodiode PD1 and the organic photoelectricconversion unit 39, the first photodiode PD1 and the organicphotoelectric conversion unit 39 are very close to each other. Ofcourse, the first photodiode PD1 and the second photodiode PD2 are veryclose to each other. That is, the dependence on the red, green, and blueF number s is suppressed. Therefore, even when the F number s arechanged, the spectral balance of each color is not changed. That is, itis possible to suppress the variation in sensitivity between the colors.

At the time of accumulating the charges, the negative voltage VL isapplied to the lower electrode 38 a of the organic photoelectricconversion unit 39. Therefore, the hole concentration of the p-typesemiconductor region. 28 serving as the hole accumulation layer of thefirst photodiode PD1 shows a tendency to increase. Accordingly, it ispossible to prevent the dark current from occurring in the interfaceswith the insulating layer 34 of the p-type semiconductor region 28.

The voltage VL of the lower electrode is set to a voltage (VL>0 V)higher than 0 V and the voltage VU of the upper electrode is set to avoltage (VU>VL) lower than the voltage VL of the lower electrode toaccumulate the charges, the hole concentration of the hole accumulationlayer of the first photodiode PD1 shows a tendency to decrease.Therefore, the hole accumulation state of the hole accumulation layerbecomes weak, and thus the dark current may easily occur. In this case,of the pairs of the electrons and holes subjected to the photoelectricconversion by the organic photoelectric conversion layer, the electronsserving as the signal charges flow to the lower electrode and areaccumulated in the charge accumulation layer. At this time, it isnecessary to form a charge accumulation layer in the end of theconductive plug to which the lower electrode is connected.

In this embodiment, since a hafnium oxide (HfO₂) layer with a negativefixed charge shown in FIG. 2 used as the insulating layer 34 on thefirst photodiode PD1 the hole accumulation state is enhanced in thep-type semiconductor region 28 serving as the hole accumulation layer.Since the hole accumulation state can be further enhanced by permittingthe lower electrode 38 a of the organic photoelectric conversion unit 39to become a negative potential, it is possible to further suppress thedark current in the interface between the silicon and the insulatinglayer.

In this embodiment, since the red, green, and blue photoelectricconversion units are laminated in one pixel, a color filter is notnecessary. Therefore, there is no loss of the incident light and it ispossible to improve sensitivity. Moreover, since the red, green, andblue signals can be obtained from the same pixel, an interpolationprocess between pixels is not necessary. Therefore, a false color doesnot occur.

In the front-illuminated solid-state imaging device, when a photodiodeserving as an organic photoelectric conversion unit is formed on amulti-layer wiring layer and photoelectric conversion unitscorresponding two colors are formed in a semiconductor substrate, onlythe aperture ratio of the organic photoelectric conversion unit may beincreased and the aperture ratios of the photodiodes for the other twocolors may be decreased. In this embodiment, however, by configuring theback-illuminated solid-state imaging device, it is possible to improvenot only the aperture ratio of the organic photoelectric conversion unitbut also the aperture ratios of the two photodiodes in the semiconductorsubstrate. Therefore, the solid-state imaging device according to thisembodiment can increase the sensitivity, compared to a case wherephotodiodes corresponding three colors are simply laminated.

In this embodiment, the potential of the upper electrode 37 is set to apositive potential and the potential of the lower electrode 38 a is setto a negative potential. However, the potential of the lower electrode38 a may be set to a positive weak potential lower than the potential ofthe upper electrode 37. Even in this case, the electrons serving as thesignal charge can be, obtained from the upper electrode 37 and can beread via the transmission transistor. Tr11.

Exemplary Method of Manufacturing Solid-State Imaging Device

FIGS. 6 to 17 are diagrams illustrating a method of manufacturing thesolid-state imaging device 21 according to the first embodiment. In thedrawings, only the major units corresponding to one pixel are shown.

First, as shown in FIG. 6 , there is prepared a so-called SOI substrate66 in which a silicon layer 22 is formed on a silicon base substrate 64with a silicon oxide layer 65 interposed therebetween. The silicon layer22 corresponds to the above-described semiconductor substrate 22. Thesilicon layer 22 is formed on an n-type silicon layer.

Subsequently, as shown in FIG. 7 , a pair of conductive plugs 45 and 46formed through the silicon layer 22 is formed in the silicon layer 22corresponding to one pixel. The conductive plugs 45 and 46 may be formedby a conductive impurity semiconductor layer formed by ion-implanting,for example, or a through via structure in which an insulating layerSiO₂ or SiN, a barrier metal Tin, and tungsten (W) are buried.

Subsequently, the first photodiode PD1 for a second color and the secondphotodiode PD2 for a third color are laminated at positions of differentdepths in the silicon layer 22 in this embodiment, the first photodiodePD1 is formed as a photodiode absorbing blue-wavelength light. Thesecond photodiode PD2 is formed as a photodiode absorbing red-wavelengthlight.

Although not shown, the plural pixel transistors including thetransmission transistors Tr11 to Tr13 are formed and the peripheralcircuit such as a logic circuit is formed in the peripheral circuitsection. The first photodiode PD1 is formed on the side of the rearsurface 23 of the silicon layer 22 by ion-implanting the p-typesemiconductor region 34 serving as the hole accumulation layer and then-type semiconductor region 29 serving as the charge accumulation layerso as to have a pn junction. The p-type semiconductor region 28 and then-type semiconductor region 29 are formed so as to have the extensionportion 28 a and 29 a extending from one ends of the p-typesemiconductor region 28 and the n-type semiconductor region 29 to thefront surface 24, respectively. The second photodiode PD2 is formed onthe side of the front surface 24 of the silicon layer 22 byion-implanting the n-type semiconductor region 32 serving as the chargeaccumulation layer so as to have a pn junction. The second photodiodePD2 is formed by the n-type semiconductor region 32 and thesemiconductor region 31 of the lower layer. The n-type semiconductorregion 32 is formed so as to have the extension portion 32 a extendingfrom one end of the n-type semiconductor region 32 to the front surface24.

The transmission transistor Tr11 is formed so as to have the n-typesemiconductor region 48 serving as the floating diffusion unit (FD) andthe transmission gate electrode 49 with the gate insulating layerinterposed therebetween (see FIG. 4 ). The transmission transistor Tr12is formed so as to have the n-type semiconductor region 51 serving asthe floating diffusion unit (FD) and the transmission gate electrode 52with the gate insulating layer interposed therebetween (see FIG. 3 ).The transmission transistor Tr13 is formed so as to have the n-typesemiconductor region 53 serving as the floating diffusion unit (FD) andthe transmission gate electrode 54 with the gate insulating layerinterposed therebetween (see FIG. 3 ).

The n-type semiconductor region 47 serving as the charge accumulationlayer is formed on the side of the front surface 24 of the silicon layer22 so as to be connected to the conductive plug 46 (see FIG. 4 ), Inthis case, the conductive plug 46 is formed so as to reach to the n-typesemiconductor region 47 and so as not to completely penetrate thesilicon layer 22. The n-type semiconductor regions 47, 48, 51, and 53may be formed simultaneously by the same ion-implanting process.Moreover, the p-type semiconductor region 50 serving as the holeaccumulation layer is formed (see FIGS. 3 and 4 ).

Subsequently, as shown in FIG. 8 , the multi-layer wiring layer 58including the wirings 57 of plural layers is formed on the front surface24 of the silicon layer 22 with the inter-layer insulating layer 56interposed therebetween.

In this embodiment, the photodiodes absorbing blue and red-wavelengthlight are used as the first photodiode PD1 and the second photodiodePD2. However, the color the configuration is not limited to the blue andred colors.

Subsequently, as shown in FIG. 9 , the supporting substrate 59 isattached to the multi-layer wiring layer 58. For example, a siliconsubstrate may be used as the supporting substrate 59.

Subsequently, as shown in FIG. 10 , the silicon base substrate 64 andthe silicon oxide layer 65 of the initial 901 substrate 66 are removedto expose the rear surface 23 of the thin silicon layer 22.

Subsequently, as shown in FIG. 11 , the insulating layer 34 is formed onthe rear surface 23 of the silicon layer It is desirable that theinterface state of the insulating layer 34 is low to suppress the darkcurrent from occurring from the interface between the silicon layer 22and the insulating layer 34 by reducing the interface, state with thesilicon layer 22. As the insulating layer 34, there may be used thelayer having the lamination structure in which the hafnium oxide (HfO₂)layer formed by ALD (Atomic layer deposition), for example, and thesilicon oxide (SiO₂) layer formed by plasma CVD (Chemical VaporDeposition) are laminated, as described in FIG. 2 .

Subsequently, as shown in FIG. 12 , contact holes 67 and 68 are formedin the insulating layer 34 so as to face the conductive plugs 45 and 46,respectively. Subsequently, the lower electrode 38 is formed on theinsulating layer 34 so as to be connected to the conductive plugs 45 and46 facing the contact holes 67 and 68, respectively. The lower electrode38 is formed of a transparent conductive layer such as ITO, since lighthas to pass through the lower electrode 38. Subsequently, the lowerelectrode 38 is selectively etched to be separated in each pixel and tobe halved in one pixel. That is, the lower electrode 38 is separatedinto the lower electrode 38 a and the lower electrode 38 b. When theelectrode from which the signal charges are obtained is separated ineach pixel, the electrode from which the charges with no signal areobtained may be connected to the entire pixel region. The lowerelectrode 38 a to which the conductive plug 45 is connected is formedbroadly so as to face the photodiodes PD1 and PD2 of the lower layer.The ITO layer may be patterned by dry etching or wet etching. In the dryetching, a mixture etching gas of, for example, Cl₂, Bcl₃, and Ar may beused. In the wet etching, an etchant such as a phosphoric acid solutionor a mixture solution of oxalic acid and phosphoric acid may be used.

Subsequently, as shown in FIG. 13 , the insulating layer 41 is formed toreduce the step difference, between the lower electrodes 38 a and 38 bAtaper angle θ1 of the bottom of the insulating layer 41 is preferably30° or less Specifically, the desired taper angle can be obtained byforming the taper angle with a photosensitive insulating layer orsubjecting a silicon oxide (SiO₂) layer formed by CVD to etch back usinga tapered resist mask.

Subsequently, as shown in FIG. 14 , the organic photoelectric conversionlayer 36 is formed on the entire surface including the insulating layer34. The upper electrode 37 is formed on the organic photoelectricconversion layer 36. In thin embodiment, the organic photoelectricconversion layer 36 is formed to execute photoelectric conversion ongreen-wavelength light. The above-described quinacridone layer, forexample, may be used as the organic layer executing the photoelectricconversion on green-wavelength light. The quinacridone layer may beformed by vacuum deposition. It is necessary to make the upper electrode37 transparent. Therefore, an ITO layer formed by a sputter method, forexample, may be used as the upper electrode 37.

Subsequently, as shown in FIG. 15 , the upper electrode 37 and theorganic photoelectric conversion layer 36 are patterned so that thelamination layer of the upper electrode 37 and the organic photoelectricconversion layer 36 remain in each pixel. By this patterning, theconductive plug 46 is connected to the upper electrode 37 so as tosupply a necessary potential to the upper electrode 37. The patterningis performed by dry etching so as to be terminated on the insulatinglayer 41.

Subsequently, as shown in FIG. 16 , in order to protect the sidewallsurface of the organic photoelectric conversion layer 36 removed by theetching, the protective insulating layer 42 is formed so as to cover thesidewall surfaces of the organic photoelectric conversion layer 36 andthe upper electrode 37.

Subsequently, as shown in FIG. 17 , the contact metal layer 43connecting the upper electrode 37 to the lower electrode 38 b connectedto the conductive plug 46 is formed so as to cover the protectiveinsulating layer 42. The respective different potentials may be suppliedto the upper electrode 37 and the lower electrode 38 a via theconductive plugs 45 and 46, respectively.

Subsequently, the on-chip lens 62 is formed on the surface including theorganic photoelectric conversion unit 39 with the planarization layer 61interposed therebetween to obtain the desired solid-state imaging device21 shown in FIG. 1 .

According to the method of manufacturing the solid-state imaging deviceof this embodiment, it is possible to manufacture the back-illuminatedsolid-state, imaging device in which the laminated organic photoelectricconversion unit 39 for one color is close to the photodiodes PD1 and PD2for two colors. That is, the organic photoelectric conversion unit 39can be formed on the upper layer of the photodiodes PD1 and PD2 withoutinterposing the multi-layer wiring layer 58. Accordingly, it is possibleto suppress the dependence on the red, green, and blue F numbers. It ispossible to manufacture the solid-state imaging device capable ofsuppressing the variation in the sensitivity between the colors withoutthe variation in the spectral balance of each color even when the Fnumbers are changed.

3. Second Embodiment Exemplary Configuration of Solid-State ImagingDevice

In FIG. 18 , a solid-state imaging device according to a secondembodiment of the invention is shown. The solid-state imaging deviceaccording to this embodiment is a CMOS solid-state imaging device. FIG.18 is a sectional view illustrating one pixel 20 in the pixel section ofthe CMOS solid-state imaging device.

A solid-state imaging device 71 according to the second embodiment is amodified example of the first embodiment. In the solid-state imagingdevice, the insulating layer 42 protecting the sidewall of the organicphotoelectric conversion layer 36 is omitted. The upper electrode 37 ofthe organic photoelectric conversion unit 39 extends to be directlyconnected to the other lower electrode 38 b. The other configuration isthe same as that described in the first embodiment. The same referencenumerals are given to the units corresponding to those in FIG. 1 , andthe repeated description is omitted.

The operation (driving method) of the solid-state imaging device 71according to the second embodiment is the same as that of the firstembodiment.

In the solid-state imaging device 71 according to the second embodiment,as in the above-described first embodiment, the organic photoelectricconversion unit 39 is close to the two photodiodes PD1 and PD2.Therefore, the dependence on the F numbers of the colors is suppressed.

Even when the F numbers are changed, it is possible to suppress thevariation in the sensitivity between the colors without the variation inthe spectral balance of each color. Moreover, since the negative,voltage is applied to the lower electrode 38 a at the time ofaccumulating the charges, the interface with the silicon insulatinglayer 34 becomes the hole accumulation state. When the insulating layer34 has the negative fixed charges, the hole accumulation state isfurther enhanced and thus it is possible to suppress the dark current.The same advantages as those of the first embodiment are obtained.

Since the protective, insulating layer 42 formed in the first embodimentis omitted and the upper electrode 37 is directly connected to the otherlower electrode 38 b the manufacturing process can be simplified.

Exemplary Method of Manufacturing Solid-State Imaging Device

FIGS. 19 to 29 are diagrams illustrating a method of manufacturing thesolid-state imaging device 71 according to the second embodiment. In thedrawings, only the major units corresponding to one pixel are shown.Processes shown in FIGS. 19 to 26 are the same as the processes of thefirst embodiment shown in FIGS. 6 to 13 .

First, as shown in FIG. 19 , there is prepared a so-called SOI substrate66 in which a silicon layer 22 is formed on a silicon base substrate 64with a silicon oxide layer 65 interposed therebetween. The silicon layer22 corresponds to the above-described semiconductor substrate 22. Thesilicon layer 22 is formed on an n-type silicon layer.

Subsequently, as shown in FIG. 20 , a pair of conductive plugs 45 and 46formed through the silicon layer 22 are formed in the silicon layer 22corresponding to one pixel. The conductive plugs 45 and 46 may be formedby a conductive impurity semiconductor layer formed by ion-implanting ora through via structure in which an insulating layer SiO₂ or SiN, abarrier metal TIN, and tungsten (W) are buried.

Subsequently, the first photodiode PD1 for a second color and the secondphotodiode PD2 for a third color are laminated at positions of differentdepths in the silicon layer 22. In this embodiment, the first photodiodePD1 is formed as a photodiode absorbing blue-wavelength light. Thesecond photodiode PD2 is formed as a photodiode absorbing red-wavelengthlight.

The plural pixel transistors including the transmission transistors Tr11to Tr13 are formed and, although not shown, the peripheral circuit suchas a logic circuit is formed in the peripheral circuit section. Thefirst photodiode PD1 is formed on the side of the rear surface 23 of thesilicon layer 22 by ion-implanting the p-type semiconductor region 34serving as the hole accumulation layer and the n-type semiconductorregion 29 serving as the charge accumulation layer so as to have a pnjunction. The p-type semiconductor region 28 and the n-typesemiconductor region 29 are formed so as to have the extension portion28 a and 29 a extending from one ends of the p-type semiconductor region28 and the n-type semiconductor region 29 to the front surface 24,respectively. The second photodiode PD2 is formed on the side of thefront surface 24 of the silicon layer 22 by ion-implanting the n-typesemiconductor region 32 serving as the charge accumulation layer so asto have a pn junction. The second photodiode PD2 is formed by the n-typesemiconductor region 32 and the semiconductor region 31 of the lowerlayer. The n-type semiconductor region 32 is formed so as to have theextension portion 32 a extending from one end of the n-typesemiconductor region 32 to the front surface 24.

The transmission transistor Tr11 is formed so as to have the n-typesemiconductor region 48 serving as the floating diffusion unit (FD) andthe transmission gate electrode 49 with the gate insulating layerinterposed therebetween. The transmission transistor. Tr12 is formed soas to have the n-type semiconductor region 51 serving as the floatingdiffusion unit (FD) and the transmission gate electrode 52 with the gateinsulating layer interposed therebetween. The transmission transistorTr13 is formed so as to have the n-type semiconductor region 53 servingas the floating diffusion unit (FD) and the transmission gate electrode54 with the gate insulating layer interposed therebetween.

The n-type semiconductor region 47 serving as the charge accumulationlayer is formed on the side of the front surface 24 of the silicon layer22 so as to be connected to the conductive plug 46. In this case, theconductive plug 46 is formed so as to reach to the n-type semiconductorregion 47 and so as not to completely penetrate the silicon layer 22.The n-type semiconductor regions 47, 48, 51, and 53 may be formedsimultaneously by the same ion-implanting process.

Subsequently, as shown in FIG. 21 , the multi-layer wiring layer 58, inwhich the wirings 57 of plural layers are disposed with the inter-layerinsulating layer 56 interposed therebetween, is formed on the frontsurface 24 of the silicon layer 22.

In this embodiment, the photodiodes absorbing blue and red-wavelengthlight are used as the first photodiode PD1 and the second photodiodePD2. However, the color the configuration is not limited to the blue andred colors.

Subsequently, as shown in FIG. 22 , the supporting substrate 59 isattached to the multi-layer wiring layer 58. For example, a siliconsubstrate may be used as the supporting substrate 59.

Subsequently, as shown in FIG. 23 , the silicon base substrate 64 andthe silicon oxide layer 65 of the initial SOI substrate 66 are removedto expose the rear surface 23 of the thin silicon layer 22.

Subsequently, as shown in FIG. 24 , the insulating layer 34 is formed onthe rear surface 23 of the silicon layer 22. It is desirable that theinterface state of the insulating layer 34 is low to suppress the darkcurrent from occurring from the interface between the silicon layer 22and the insulating layer 34 by reducing the interface state with thesilicon layer 22. As the insulating layer 34, there may be used thelayer having the lamination structure in which the hafnium oxide (HfO₂)layer formed by ALD (Atomic layer deposition), for example, and thesilicon oxide (SiO₂) layer formed by plasma CVD (Chemical VaporDeposition) are laminated, as described in FIG. 2 .

Subsequently, as shown in FIG. 25 , the contact holes 67 and 68 areformed in the insulating layer 34 so as to face the conductive plugs 45and 46, respectively. Subsequently, the lower electrode 38 is formed onthe insulating layer 34 so as to be connected to the conductive plugs 45and 46 facing the contact holes 67 and 68, respectively. The lowerelectrode 38 is formed of a transparent conductive layer such as ITO,since light has to pass through the lower electrode 38. Subsequently,the lower electrode 38 is selectively etched to be separated in eachpixel and to be halved in one pixel. That is, the lower electrode 38 isseparated into the lower electrode 38 a and the lower electrode 38 b.The lower electrode 38 a to which the conductive plug 45 is connected isformed broadly so as to face the photodiodes PD1 and PD2 of the lowerlayer.

Subsequently, as shown in FIG. 26 , the insulating layer 41 is formed toreduce the step difference between the lower electrodes 38 a and 38 bAtaper angle θ1 of the bottom of the insulating layer 41 is preferably30° or less. Specifically, the desired taper angle can be obtained byforming the taper angle with a photosensitive insulating layer orsubjecting a silicon oxide (SiO₂) layer formed by CVD to etch back usinga tapered resist mask.

The above-described manufacturing method is the same as themanufacturing method of the first embodiment. In this embodiment, asshown in FIG. 27 , the organic photoelectric conversion layer 36 isformed on the entire surface including the lower electrodes 28 [28 a and28 b] and the insulating layer 41. In this embodiment, the organicphotoelectric conversion layer 36 is formed to execute photoelectricconversion on green-wavelength light. The above-described quinacridonelayer, for example, may be used as the organic layer executing thephotoelectric conversion on green-wavelength light. The quinacridonelayer may be formed by vacuum deposition. It is necessary to make theupper electrode 37 transparent. Therefore, an ITO layer formed by asputter method, for example, may be used as the upper electrode 37.

Subsequently, as shown in FIG. 28 , the organic photoelectric conversionlayer 36 is patterned so that the organic photoelectric conversion layer36 remains in each pixel. This patterning is stopped on the insulatinglayer 41. The patterning is performed by dry etching, as in the firstembodiment.

Subsequently, as shown in FIG. 29 , the upper electrode 37 is formed onthe entire surface including the organic photoelectric conversion layer36 so that a part of the upper electrode 37 is directly connected to thelower electrode 38 b and then the upper electrode 37 is patterned so asto be separated in each pixel. It is necessary to make the upperelectrode 37 transparent. Therefore, an ITO layer formed by a sputtermethod may be used as the upper electrode 37. The respective differentpotentials may be supplied to the upper electrode 37 and the lowerelectrode 38 a via the conductive plugs 46 and 45, respectively.

Subsequently, the on-chip lens 62 is formed on the surface including theorganic photoelectric conversion unit 39 with the planarization layer 61interposed therebetween to obtain the desired solid-state imaging device71 shown in FIG. 18 .

According to the method of manufacturing the solid-state imaging device71 of this embodiment, it is possible to manufacture theback-illuminated solid-state imaging device in which the laminatedorganic photoelectric conversion unit 39 for one color is close to thephotodiodes PD1 and PD2 for two colors. That is, the organicphotoelectric conversion unit 39 can be formed on the upper layer of thephotodiodes PD1 and PD2 without interposing the multi-layer wiring layer58. Accordingly, it is possible to suppress the dependence on the red,green, and blue F numbers. It is possible to manufacture the solid-stateimaging device capable of suppressing the variation in the sensitivitybetween the colors without the variation in the spectral balance of eachcolor even when the F numbers are changed. Since the upper electrode 37is directly connected to other the lower electrode 38 b the number ofmanufacturing processes can be reduced more, than that of the firstembodiment.

4. Third Embodiment Exemplary Configuration of Solid-State ImagingDevice

In FIG. 30 , a diagram illustrating a solid-state imaging deviceaccording to a third embodiment of the invention is shown. Thesolid-state imaging device according to this embodiment is a CMOSsolid-state imaging device. FIG. 30 is a sectional view illustrating onepixel 20 in the pixel section of the CMOS solid-state imaging device.

A solid-state imaging device 73 according to the third embodiment hasthe same configuration as that of the first embodiment. The holes areread as the signal charges from the organic photoelectric conversionunit 39 and the electrons are read as the signal charges from the twofirst photodiode PD1 and second photodiode PD2. The holes of the signalcharges in the organic photoelectric conversion unit 39 are configuredso as to be read from the upper electrode 37. That is, as describedabove, the solid-state imaging device 73 according to this embodiment isthe back-illuminated solid-state imaging device in which the organicphotoelectric conversion unit 39, the first photodiode PD1 and thesecond photodiode PD2 are laminated in the depth direction in one pixel.The first photodiode PD1 for the second color and the second photodiodePD2 for the third color are formed at the positions of different depthsin the semiconductor substrate 22. The organic photoelectric conversionunit 39 for the first color is laminated on the upper layer of thesemiconductor substrate 22 with the insulating layer 34 interposedtherebetween, so as to be close to the second photodiode PD2. In thisembodiment, the solid-state imaging device includes the organicphotoelectric conversion unit 39 executing the photoelectric conversionto the green-wavelength light, the first photodiode PD1 executing thephotoelectric conversion to the blue-wavelength light, and the secondphotodiode PD2 executing the photoelectric conversion to thered-wavelength light.

The organic photoelectric conversion unit 39 includes the organicphotoelectric layer 36 and includes the lower electrode 38 a and theupper electrode 37 which interpose the organic photoelectric conversionlayer 36. The lower electrode 38 a is connected to the conductive plug45. The upper electrode 37 is connected to the other conductive plug 46with the contact metal layer 43 and the other lower electrode 38 binterposed therebetween.

In this embodiment, of the pairs of the electrons and holes generated bythe photoelectric conversion by the organic photoelectric conversionunit 39, the holes serving as the signal charges are guided andaccumulated on the side of the front surface 34 of the substrate.Therefore, the p-type semiconductor region 74 serving as theaccumulation layer is formed on the side of the front surface 24 of thesubstrate. The p-type semiconductor region 75 forms the floatingdiffusion unit (FD) to which the signal charges (holes) of the p-typesemiconductor region 74 are transmitted via the transmission transistorTr11. The other conductive plug 46 connected to the upper electrode 37is formed so as to reach to the p-type semiconductor region 74 servingas the charge accumulation layer. When the conductive plugs 45 and 46are formed in an impurity semiconductor layer by ion implanting, theconductive lugs and 46 are formed in the p-type semiconductor layer.

The first photodiode PD1 and the second photodiode PD2 use the electronsof the pairs of the electrons and holes generated by the photoelectricconversion as the signal charges. Therefore, the n-type semiconductorregions 51 and 53 form the floating diffusion units (FD) to which thesignal charges (electrons) of the first photodiode PD1 and the secondphotodiode PD2 are transmitted via the transmission transistors Tr12 andTr13, respectively.

As in the first embodiment, the pixel transistors having thecross-section different from that in FIG. 30 are schematicallyillustrated in FIGS. 31 and 32 . In FIGS. 31 and 32 , the transmissiontransistors among the plural pixel transistors are representativelyshown. That is, in the organic photoelectric conversion unit 39, asshown in FIG. 32 , the p-type semiconductor region 74 for chargeaccumulation is connected to the transmission transistor Tr11 having then-type semiconductor region serving as the floating diffusion unit andthe transmission gate electrode 49. In the first photodiode PD1, asshown in FIG. 31 , the extension portion 29 a of the n-typesemiconductor region 29 serving as the charge accumulation layer isconnected to the transmission transistor Tr12 including the n-typesemiconductor region 51 serving as the floating diffusion unit and thetransmission gate electrode 52. In the second photodiode PD2 as shown inFIG. 31 , the extension portion 32 a of the n-type semiconductor region32 serving as the charge accumulation layer is connected to thetransmission transistor Tr13 including the n-type semiconductor region53 serving as the floating diffusion unit and the transmission gateelectrode 54.

At least, a p-type semiconductor region 50 serving as the holeaccumulation layer is formed in the interface with the insulating layer,which faces the front surface 24 of the substrate of the n-typesemiconductor regions 29 a and 32 a respectively forming the firstphotodiode. PD1 and the second photodiode PD2. In FIG. 31 , the p-typesemiconductor region 50 serving as the hole accumulation layer is formedso as to include the interface between the p-type semiconductor region33 and the insulating layer. The re-type semiconductor region 70 servingas the electron accumulation layer is formed in the interface with theinsulating layer, which faces the front surface 24 of the substrate ofthe p-type semiconductor region 74 for charge accumulation in theorganic photoelectric conversion unit.

The other configuration is the same as that of the first embodiment. Thesame reference numerals are given to the units corresponding to theunits in FIG. 1 , and the repeated description is omitted.

An operation (driving method) of the solid-state imaging device 73according to the third embodiment will be described. The solid-stateimaging device 73 is configured as a back-illuminated solid-stateimaging device emitting light from the rear surface of the substrate. Inthis embodiment, a negative voltage VL (<0 V) is applied to the lowerelectrode 38 a of the organic photoelectric conversion unit 39, and anupper voltage VU (<VL) lower than the lower voltage VL is applied to theupper electrode 37. The upper voltage VU applied to the upper electrode37 reading a signal is applied to the necessary wiring 57 via theconductive plug 46. The negative voltage VL applied to the lowerelectrode 38 a of the organic photoelectric conversion unit 39 isnegative at the time of reset. The voltage of 0 V is applied from thenecessary wiring 57 to the p-type semiconductor region 28 serving as thehole accumulation layer via the extension portion 28 a.

When light is incident on one pixel 20 without passing through a colorfilter at the time of accumulating the charges, green-wavelength lightis subjected to photoelectric conversion by the organic photoelectricconversion unit 39. Of the pairs of the electrons and holes generated bythe photoelectric conversion, the holes serving as the signal chargesare guided to the upper electrode 37 with the potential VU (<VL) lowerthan the lower voltage VL and are accumulated in the p-typesemiconductor region 74 serving as the charge accumulation layer via theconductive plug 46. The electrons subjected to the photoelectricconversion are guided to the lower electrode 38 a with the negative,voltage VL (<0) higher than the upper potential VU and are, dischargedvia the conductive plug 45 and the necessary wiring 57. Theblue-wavelength light is absorbed and subjected to photoelectricconversion by the first photodiode PD1 formed in a shallow portion closeto the rear surface of the semiconductor substrate 22, and the signalcharges corresponding to the blue color are accumulated in the n-typesemiconductor region 29. The red-wavelength light is absorbed andsubjected to photoelectric conversion by the second photodiode PD2formed in a deep portion from the rear surface of the semiconductorsubstrate 22, and the signal charges corresponding to the red color areaccumulated in the n-type semiconductor region 32.

At the time of reading the signals, the green signal charges (holes)accumulated in the p-type semiconductor region 74 are transmitted to thep-type semiconductor region serving as the floating diffusion unit (FD),when the transmission transistor Tr11 is turned on. The blue signalcharges (electrons) accumulated in the n-type semiconductor region 29are transmitted to the n-type semiconductor region 51 serving as thefloating diffusion unit (FD), when the transmission transistor Tr12 isturned on. The red signal charges (electrons) accumulated in the n-typesemiconductor region 32 are transmitted to the n-type semiconductorregion 53 serving as the floating diffusion unit (FD), when thetransmission transistor Tr13 is turned on. The red, green, and bluepixel signals are read and output to the vertical signal lines via theother pixel transistors.

In the solid-state imaging device 73 according to the third embodiment,as in the above-described embodiments, the organic photoelectricconversion unit 39 is close to the two photodiodes PD1 and PD2. Evenwhen the dependence on the F numbers of the colors is suppressed and theF numbers are changed, it is possible to suppress the variation in thesensitivity between the colors without the variation in the spectralbalance of each color. Since the negative voltage VL (<0 V) is appliedto the lower electrode 38 a at the time of accumulating the charges, theinterface with the silicon insulating layer 34 becomes the holeaccumulation state. When the insulating layer 34 has the negative fixedcharges, the hole accumulation state is further enhanced and it ispossible to suppress the dark current.

In the third embodiment, the upper electrode 37 of the organicphotoelectric conversion unit 39 is connected to the lower electrode 38b via the contact metal layer 43, as in the first embodiment. The upperelectrode 37 according to the second embodiment may be directlyconnected to the other lower electrode 38 b.

5. Fourth Embodiment Exemplary Configuration of Solid-State ImagingDevice

In FIG. 33 , a solid-state imaging device according to a fourthembodiment of the invention is shown. The solid-state imaging deviceaccording to this embodiment is a CMOS solid-state imaging device. FIG.33 is a sectional view illustrating one pixel 20 in the pixel section ofthe CMOS solid-state imaging device.

A solid-state imaging device 75 according to the fourth embodiment hasthe same configuration as that of the first embodiment. However, thesignal charges (electrons) from the organic photoelectric conversionunit 39 are read from the lower electrode 38 a. The signal charges(electrons) from the two first photodiode PD1 and second photodiode PD2are read as in the first embodiment. That is, the solid-state imagingdevice 75 according to this embodiment is the back-illuminatedsolid-state imaging device in which the organic photoelectric conversionunit 39, the first photodiode PD1, and the second photodiode PD2 arelaminated in the depth direction in one pixel. The first photodiode PD1for the second color and the second photodiode PD2 for the third colorare formed at the positions of different depths in the semiconductorsubstrate 22. The organic photoelectric conversion unit 39 for the firstcolor is laminated on the upper layer of the semiconductor substrate 22with the insulating layer 34 interposed therebetween so as to be closeto the second photodiode PD2. In this embodiment, the solid-stateimaging device includes the organic photoelectric conversion unit 39executing the photoelectric conversion to the green-wavelength light,the first photodiode PD1 executing the photoelectric conversion to theblue-wavelength light, and the second photodiode PD2 executing thephotoelectric conversion to the red-wavelength light.

The organic photoelectric conversion unit 39 includes the organicphotoelectric layer 36 and includes the lower electrode 38 a and theupper electrode 37 which interpose the organic photoelectric conversionlayer 36. The lower electrode 38 a is connected to the conductive plug45. The upper electrode 37 is connected to the other conductive plug 46with the contact metal layer 43 and the other lower electrode 38 binterposed therebetween.

In this embodiment, since the electrons serving as the signal chargesgenerated by the photoelectric conversion by the organic photoelectricconversion unit 39 are read via the lower electrode 38 a the n-typesemiconductor region 47 serving as the charge accumulation layer isformed on the front surface 24 of the substrate on the side of theconductive plug 45 connected to the lower electrode 38 a. The n-typesemiconductor region 48 serving as the floating diffusion unit (FD) isformed on the front surface 24 of the substrate so as to be close, tothe n-type semiconductor region 47.

Since the other configuration is the same as that of the firstembodiment, the same reference numerals are given to the unitscorresponding to the unit in FIG. 1 and the repeated description isomitted. The different cross-sections of the transmission transistorsTr11 to Tr13 from those in FIG. 33 are illustrated. However, in FIG. 33, the gate electrodes 49, 52, and 54 are schematically illustrated forconvenience.

An operation (driving method) of the solid-state imaging device 75according to the fourth embodiment will be described. The solid-stateimaging device 75 is configured as a back-illuminated solid-stateimaging device emitting light from the rear surface of the substrate. Inthis embodiment, a negative voltage VL (<0 V) is applied to the lowerelectrode 38 a of the organic photoelectric conversion unit 39, and anupper voltage VU (<VL) lower than the lower voltage VL is applied to theupper electrode 37. The upper voltage VU is given from the necessarywiring 57 on the front surface of the substrate via the conductive plug45. The voltage of 0 V is applied from the necessary wiring 57 to thep-type semiconductor region 28 serving as the hole accumulation layervia the extension portion 28 a.

When light is incident on one pixel 20 without passing through a colorfilter at the time of accumulating the charges, green-wavelength lightis subjected to photoelectric conversion by the organic photoelectricconversion unit 39. Of the pairs of the electrons and holes generated bythe photoelectric conversion, the electrons serving as the signalcharges are guided to the lower electrode 38 a with the potential VL(<VU) higher than the upper voltage VU and are accumulated in the n-typesemiconductor region 47 serving as the charge, accumulation layer viathe conductive plug 45. The holes subjected to the photoelectricconversion are guided to the upper electrode 37 with the potential VU(<VL) lower than the lower potential VL and are discharged via theconductive plug 46 and the necessary wiring 57. The blue-wavelengthlight is absorbed and subjected to photoelectric conversion by the firstphotodiode PD1 formed in a shallow portion close to the rear surface ofthe semiconductor substrate 22, and the signal charge corresponding tothe blue color are accumulated in the n-type semiconductor region 29.The red-wavelength light is absorbed and subjected to photoelectricconversion by the second photodiode PD2 formed in a deep portion fromthe rear surface of the semiconductor substrate 22, and the signalcharges corresponding to the red color are accumulated in the n-typesemiconductor region 32.

At the time of reading the charges, the transmission transistors Tr11,Tr12, and Tr13 are turned on. When the transmission transistors areturned on, the accumulated signal charges (electrons) of the organicphotoelectric conversion unit 39, the first photodiode PD1, and thesecond photodiode PD2 are transmitted to the floating diffusion units(FD) 48, 51, and 54, respectively. The red, green, and blue pixelsignals are read and output to the vertical signal line via the otherpixel transistors.

In the solid-state imaging device 75 according to the fourth embodiment,as in the above-described embodiments, the organic photoelectricconversion unit 39 is close to the two photodiodes PD1 and PD2. Evenwhen the dependence on the F numbers of the colors is suppressed and theF numbers are changed, it is possible to suppress the variation in thesensitivity between the colors without the variation in the spectralbalance of each color. Since the negative voltage VL (<0 V) is appliedto the lower electrode 38 a at the time of accumulating the charges, theinterface with the silicon insulating layer 34 becomes the holeaccumulation state. When the insulating layer 34 has the negative fixedcharges, the hole accumulation state is further enhanced and it ispossible to suppress the dark current.

6. Fifth Embodiment Exemplary Configuration of Solid-State ImagingDevice

In FIG. 34 , a solid-state imaging device according to a fifthembodiment of the invention is shown. The solid-state imaging deviceaccording to this embodiment is a CMOS solid-state imaging device. FIG.34 is a sectional view illustrating one pixel 20 in the pixel section ofthe CMOS solid-state imaging device.

A solid-state imaging device 77 according to the fifth embodiment hasalmost the same configuration as that of the first embodiment. However,the signal charges (holes) from the organic photoelectric conversionunit 39 are read from the lower electrode 38 a. The signal charges(electrons) from the two first photodiode PD1 and second photodiode PD2are read as in the first embodiment. That is, the solid-state imagingdevice 77 according to this embodiment is the back-illuminatedsolid-state imaging device in which the organic photoelectric conversionunit 39, the first photodiode PD1 and the second photodiode PD2 arelaminated in the depth direction in one pixel. The first photodiode PD1for the second color and the second photodiode PD2 for the third colorare formed at the positions of different depths in the semiconductorsubstrate 22. The organic photoelectric conversion unit 39 for the firstcolor is laminated on the upper layer of the semiconductor substrate 22with the insulating layer 34 interposed therebetween so as to be closeto the second photodiode PD2. In this embodiment, the solid-stateimaging device includes the organic photoelectric conversion unit 39executing the photoelectric conversion to the green-wavelength light,the first photodiode PD1 executing the photoelectric conversion to theblue-wavelength light, and the second photodiode PD2 executing thephotoelectric conversion to the red-wavelength light.

The organic photoelectric conversion unit 39 includes the organicphotoelectric layer 36 and includes the lower electrode 38 a and theupper electrode 37 which interpose the organic photoelectric conversionlayer 36. The lower electrode 38 a is connected to the conductive plug45. The upper electrode 37 is connected to the other conductive plug 46with the contact metal layer 43 and the other lower electrode 38 binterposed therebetween.

In this embodiment, of the pairs of the electrons and holes generated bythe photoelectric conversion by the organic photoelectric conversionunit 39, the holes serving as the signal charges are guided andaccumulated on the side of the front surface 34 of the substrate.Therefore, the p-type semiconductor region 74 serving as the chargeaccumulation layer is formed on the side of the front surface 24 of thesubstrate. The p-type semiconductor region 75 forms the floatingdiffusion unit (FD) to which the signal charges (holes) of the p-typesemiconductor region 74 are transmitted via the transmission transistorTr11. The other conductive plug 45 connected to the lower electrode 38 ais formed so as to reach to the p-type semiconductor region 74 servingas the charge accumulation layer. When the conductive plugs 45 and 46are formed in the impurity semiconductor layer by ion implanting, theconductive plugs 45 and 46 are formed in the p-type semiconductor layer.

The first photodiode PD1 and the second photodiode PD2 use the electronsof the pairs of the electrons and holes generated by the photoelectricconversion as the signal charges. Therefore, the n-type semiconductorregions 51 and 53 form the floating diffusion units (FD) to which thesignal charges (electrons) of the first photodiode PD1 and the secondphotodiode PD2 are transmitted via the transmission transistors Tr12 andTr13, respectively.

The other configuration is the same as those of the first and thirdembodiments. The same reference numerals are given to the unitscorresponding to the units in FIGS. 1 and 30 , and the repeateddescription is omitted.

An operation (driving method) of the solid-state imaging device 77according to the fifth embodiment will be described. The solid-stateimaging device 77 is configured as the back-illuminated solid-stateimaging device emitting light from the rear surface of the substrate. Inthis embodiment, the negative fixed voltage VL (<0 V) is applied to thelower electrode 38 a of the organic photoelectric conversion unit 39,and the upper voltage VU (<VL) higher than the lower voltage VL isapplied to the upper electrode 37. The voltage of 0 V is applied fromthe necessary wiring 57 to the extension portion 28 a of the p-typesemiconductor region 28 serving as the hole accumulation layer.

When light is incident on one pixel 20 without passing through a colorfilter at the time of accumulating the charges, green-wavelength lightis subjected to photoelectric conversion by the organic photoelectricconversion unit 39. Of the pairs of the electrons and holes generated bythe photoelectric conversion, the holes serving as the signal chargesare guided to the lower electrode 38 a with the negative potential VLand are accumulated in the p-type semiconductor region 74 serving as thecharge accumulation layer via the conductive plug 45. The electronssubjected to the photoelectric conversion are guided to the upperelectrode 37 with the potential VU (>VL) higher than the lower potentialVL and are discharged via the conductive plug 46 and the necessarywiring 57. The blue-wavelength light is absorbed and subjected tophotoelectric conversion by the first photodiode PD1 formed in a shallowportion close to the rear surface of the semiconductor substrate 22, andthe signal charges corresponding to the blue color are accumulated inthe n-type semiconductor region 29. The red-wavelength light is absorbedand subjected to photoelectric conversion by the second photodiode PD2formed in a deep portion from the rear surface of the semiconductorsubstrate 22, and the signal charges corresponding to the red color areaccumulated in the n-type semiconductor region 32.

At the time of reading the charges, the transmission transistors Tr11,Tr12, and Tr13 are turned on. When the transmission transistors areturned on, the accumulated signal charges. (holes) of the organicphotoelectric conversion unit 39 and the accumulated signal charges(electrons) of the first photodiode PD1 and the second photodiode PD2are transmitted to the floating diffusion units (FD) 75, 51, and 54,respectively. The pixels signals of the red, green, and blue colors areread and output to the vertical signal lines via the other pixeltransistors.

In the solid-state imaging device 77 according to the fifth embodiment,as in the above-described embodiments, the organic photoelectricconversion unit 39 is close to the two photodiodes PD1 and PD2. Evenwhen the dependence on the F numbers of the colors is suppressed and theF numbers are changed, it is possible to suppress the variation in thesensitivity between the colors without the variation in the spectralbalance of each color. Since the negative voltage VL (<0) is applied tothe lower electrode 38 a at the time of accumulating the charges, theinterface, with the silicon insulating layer 34 becomes the holeaccumulation state. When the insulating layer 34 has the negative fixedcharges, the hole accumulation state is further enhanced and it ispossible to suppress the dark current.

In the fourth and fifth embodiments, the upper electrode 37 of theorganic photoelectric conversion unit 39 is connected to the lowerelectrode 38 b via the contact metal layer 43, as in the firstembodiment. However, the upper electrode 37 may be connected directly tothe lower electrode 38 b as in the second embodiment.

7. Sixth Embodiment Exemplary Configuration of Solid-State ImagingDevice

In FIG. 35 , a solid-state imaging device according to a sixthembodiment of the invention is shown. The solid-state imaging deviceaccording to this embodiment is a CMOS solid-state imaging device. FIG.35 is a sectional view illustrating one pixel 20 in the pixel section ofthe CMOS solid-state imaging device.

The solid-state imaging device 79 according to the sixth embodiment isconfigured to read the signals of the organic photoelectric conversionunit 39 via the transmission transistors by the thin film transistor.That is, the solid-state imaging device according to the sixthembodiment is the back-illuminated solid-state, imaging device in whichthe organic photoelectric conversion unit 39, the first photodiode PD1and the second photodiode 902 are laminated in the depth direction inone pixel. The first photodiode PD1 for the second color and the secondphotodiode PD2 for the third color are formed at the positions ofdifferent depths in the semiconductor substrate 22. The organicphotoelectric conversion unit 39 for the first color is laminated on theupper layer of the semiconductor substrate 22 with the insulating layer34 interposed therebetween so as to be close to the second photodiodePD2. In this embodiment, the solid-state imaging device includes theorganic photoelectric conversion unit 39 executing the photoelectricconversion to the green-wavelength light, the first photodiode PD1executing the photoelectric conversion to the blue-wavelength light, andthe second photodiode PD2 executing the photoelectric conversion to thered-wavelength light.

The organic photoelectric conversion unit 39 includes the organicphotoelectric layer 36 and includes the lower electrode 38 and the upperelectrode 37 which interpose the organic photoelectric conversion layer36.

In this embodiment, a thin film transistor Tr14 configured to read thesignal charges of the organic photoelectric conversion unit. 39 isformed on the insulating layer 34 formed between the first photodiodePD1 and the organic photoelectric conversion unit 39 on the side of therear surface 23 of the substrate. The thin film transistor Tr14corresponds to the transmission transistor among the plural pixeltransistors. Therefore, the drain of the thin film transistor Tr14corresponds to a floating diffusion unit (FD).

The thin film transistor Tr14 is a so-called bottom gate type thin filmtransistor having a configuration with a pair of source/drain and gate.The thin film transistor Tr14 is formed by forming a gate electrode 84on the insulating layer 34, forming a gate insulating layer 85 on thegate electrode 84, and forming a semiconductor thin film (active layer)86, which has a channel region c, a source region S, and a drain regionD, on the gate insulating layer 85. The upper electrode 37 of theorganic photoelectric conversion unit 39 is connected to the sourceregion S via a contact hole of the insulating layer 88.

Conductive plugs 81, 82, and 83 formed through the substrate 22 areformed in the semiconductor substrate 22. The conductive plugs 81, 82and 83 may be formed in an impurity semiconductor layer, a metal layer,or the like by ion implanting, as described above. The lower electrode38 of the organic photoelectric conversion unit 39 is connected to theconductive plug 81. The drain region J of the thin film transistor Tr14is connected to the conductive plug 82. The gate electrode 84 of thethin film transistor Tr14 is connected to the conductive plug 83 via theconductive layer 89.

Since the other configuration is the same as the configuration describedin the first embodiment, the same reference numerals are given to theunits corresponding to the units in FIG. 1 and the repeated descriptionis omitted. The different cross-sections of the transmission transistorsTr12 and Tr13 from those in FIG. 35 are illustrated. However, in FIG. 35, the gate electrodes 52 and 54 are schematically illustrated forconvenience.

An operation (driving method) of the solid-state imaging device 79according to the sixth embodiment will be described. In this embodiment,the negative fixed voltage VL (<0 V) is applied to the lower electrode38 of the organic photoelectric conversion unit 39 via the necessarywiring 57 and the conductive plug 81, and the voltage VU (<VL), such asa power voltage VDD, higher than the voltage VL of the lower electrode38 is applied to the upper electrode 37 at the time of accumulating thecharges. The drain region D of the thin film transistor Tr14 isconnected to the source of a reset transistor (not shown) and the gateof an amplification transistor (not shown) via the necessary wiring 57.The voltage of 0 V is applied from the necessary wiring 57 to theextension portion 28 a of the p-type semiconductor region 28 serving asthe hole accumulation layer.

The potential of the upper electrode 37 at the time of accumulating thecharges becomes high due to the source potential of the thin filmtransistor Tr14.

The source potential becomes the power potential, for example, as in thefirst embodiment. When the reset transistor and the thin film transistorTr14 serving as the transmission transistor are turned on and reset, andthen both the transistors are turned off, the source potential becomesthe reset level and the potential is varied in accordance with theaccumulated charges.

When light is incident on one pixel 20 without passing through a colorfilter at the time of accumulating the charges, green-wavelength lightis subjected to photoelectric conversion by the organic photoelectricconversion layer 36. Of the pairs of the electrons and holes generatedby the photoelectric conversion, the electrons serving as the signalcharges are accumulated in the source region S of the thin filmtransistor Tr14 via the upper electrode 37. The holes subjected to thephotoelectric conversion are guided to the lower electrode 38 with thepotential VL and are discharged via the conductive, plug 81 and thenecessary wiring 57. The blue-wavelength light is subjected tophotoelectric conversion by the first photodiode PD1 formed in a shallowportion close to the rear surface of the semiconductor substrate 22, andthe signal charges (electrons) corresponding to the blue color areaccumulated in the n-type semiconductor region 29. The red-wavelengthlight is subjected to photoelectric conversion by the second photodiodePD2 formed in a deep portion from the rear surface of the semiconductorsubstrate 22, and the signal charges (electrons) corresponding to thered color are accumulated in the n-type semiconductor region 32.

At the time of reading the charges, the thin film transistor Tr14, thetransmission transistors Tr12, and Tr13 are turned on. When thetransmission transistor Tr14 is turned on, the green signal chargesaccumulated in the source region S are transmitted to the drain region Dserving as the floating diffusion unit (FD). When the other transmissiontransistors Tr12 and Tr13 are turned on, the blue and red signal chargesaccumulated in the first photodiode PD1 and the second photodiode PD2are transmitted to the n-type semiconductor regions 51 and 53 serving asthe floating diffusion units (FD), respectively. The pixels signals ofthe red, green, and blue colors are read and output to the verticalsignal lines via the other pixel transistors.

In the solid-state imaging device 79 according to the sixth embodiment,as in the above-described embodiments, the organic photoelectricconversion unit 39 is close to the two photodiodes PD1 and PD2. Evenwhen the dependence on the F numbers of the colors is suppressed and theF numbers are changed, it is possible to suppress the variation in thesensitivity between the colors without the variation in the spectralbalance of each color. Since the negative voltage VL (<0 V) is appliedto the lower electrode 38 a at the time of accumulating the charges, theinterface with the silicon insulating layer 34 becomes the holeaccumulation state. When the insulating layer 34 has the negative fixedcharges, the hole accumulation state is further enhanced and it ispossible to suppress the dark current. By providing the thin filmtransistor Tr14, the conductive plugs can be shared, as described in aseventh embodiment (FIG. 42 ), which is described below.

Exemplary Method of Manufacturing Solid-State Imaging Device

FIGS. 36 to 45 are diagrams illustrating a method of manufacturing thesolid-state imaging device 79 according to the sixth embodiment. In thedrawings, only the major units corresponding to one pixel are shown. Theprocess in FIG. 36 is the same as the process in FIG. 11 of the firstembodiment except for forming the three conductive plugs 81 to 83 andthe transmission transistors Tr12 and Tr13. That is, the configurationin FIG. 36 can be obtained by the processes in FIGS. 6 to 11 .

In FIG. 36 , the pixel transistors including the transmissiontransistors Tr12 and Tr13 are formed on the front surface of thesemiconductor substrate 22, and the peripheral circuit such as a logiccircuit is formed in the peripheral circuit section. The multi-layerwiring layer 58, in which the wirings 57 of plural layers are formedwith the inter-layer insulating layer 56 interposed therebetween, isformed in the upper portion of the front surface of the semiconductorsubstrate 22. Moreover, the supporting substrate 59 is attached. Theconductive plugs 81, 82, and 83 formed through the substrate 22 areformed in the semiconductor substrate 22. The first photodiode PD1 andthe second photodiode PD2 are laminated in the depth direction. Theinsulating layer 34 is formed on the rear surface 23 of thesemiconductor substrate 22. The insulating layer 34 can be formed of thelayer with the negative fixed charges, as described above.

Subsequently, as shown in FIG. 37 , contact holes 91, 92, and 93 areformed to expose the conductive plugs. 81, 82, and 83 to the insulatinglayer 34. Subsequently, a conductive material layer is formed andpatterned to form the gate electrode 84 at the position necessary in theinsulating layer 34, and the conductive layer 89 is simultaneouslyformed so as to be connected to the conductive plug 83 via the contacthole 93. The gate electrode 84 and the conductive layer 89 are formed ofthe same material and are continuously connected at the differentpositions. It is preferable to use low resistant material such as Al andkit as the electrode material. The conductive plug 83 connected to thegate electrode 86 is formed in the peripheral circuit section.

Subsequently, as shown in FIG. 38 , the gate insulating layer 85 isformed on the entire surface so as to cover the gate electrode 84.

Subsequently, as shown in FIG. 39 , the gate insulating layer 85 ispatterned to selectively remove the unnecessary portion of the gateinsulating layer 85 and only the extension portion to the insulatinglayer 34 remains on the front surface of the gate electrode 84. The gateinsulating layer 85 may remain up to the sidewall of the gate electrodeand may not remain above the insulating layer 84.

Subsequently, as shown in FIG. 40 , the semiconductor thin film 86 isformed on the entire surface including the gate insulating layer 85. Anamorphous silicon layer, a fine crystal silicon layer, or the like maybe used as the semiconductor thin film 86. When a transparentsemiconductor such as ZnO, TnO, SnO, or CdO is used as the semiconductorthin film 86, it is more preferable in that an aperture ratio of thephotoelectric conversion unit is improved.

Subsequently, as shown in FIG. 41 , the semiconductor thin film 86 ispatterned so that the active layer of the source region S, the channelregion C, and the drain region D remains. The drain region ID isconnected to the conductive plug 82 via the contact hole 92. The sourceregion S and the drain region U are formed as n-type impurity regions inthis embodiment.

Subsequently, as shown in FIG. 42 , the lower electrode 38 formed of atransparent conductive layer is formed on the insulating layer 34 so asto be connected to the conductive plug 81 via the contact hole 91.Subsequently, the insulating layer 88 is formed on the entire surface,and then the insulating layer 88 is patterned so that region where theorganic photoelectric conversion unit is formed and the source region Sof the semiconductor thin film (active layer) 86 face each other, andopenings 94 and 95 with a taper are formed.

Subsequently, as shown in FIG. 43 , the organic photoelectric conversionlayer 36 is formed on the entire surface so as to be adjacent on thelower electrode 38 facing the opening 94. The organic photoelectricconversion layer 36 can be formed by vapor deposition, for example.

Subsequently, as shown in FIG. 44 , the organic photoelectric conversionlayer 36 is patterned so that a part of the organic photoelectricconversion layer 36 extends on the lower electrode 38 and remains on theinsulating layer 88.

Subsequently, as shown in FIG. 45 , the upper electrode 37 formed of atransparent conductive layer is formed so as to be connected to theorganic photoelectric conversion layer 36 and the source region S of thesemiconductor thin film 86 via the opening 95.

Subsequently, the planarization layer 61 and the on-chip lens 62 areformed to form the desired solid-state imaging device 79 shown in FIG.35 .

According to the method of manufacturing the solid-state imaging deviceof this embodiment, it is possible to manufacture the back-illuminatedsolid-state imaging device in which the laminated organic photoelectricconversion unit 39 for one color is close to the photodiodes PD1 and PD2for two colors. That is, the organic photoelectric conversion unit 39can be formed on the upper layer of the photodiodes PD1 and PD2 withoutinterposing the multi-layer wiring layer. Accordingly, it is possible tosuppress the dependence on the red, green, and blue F numbers. Even whenthe F numbers are changed, it is possible to manufacture the solid-stateimaging device capable of suppressing the variation in the sensitivitybetween the colors without the variation in the spectral balance of eachcolor.

8. Seventh Embodiment Exemplary Configuration of Solid-State ImagingDevice

In FIGS. 46 and 47 , a solid-state imaging device according to a seventhembodiment of the invention is shown. The solid-state imaging deviceaccording to this embodiment is a back-illuminated CMOS solid-stateimaging device. In a solid-state imaging device 98 according to theseventh embodiment, the organic photoelectric conversion unit 39 for thefirst color, in which the thin film transistor Tr14 serves as atransmission transistor, the first photodiode PD1 for the second color,and the second photodiode PD2 for the third color are laminated in thedepth direction in the same pixel. As in the sixth embodiment, the firstphotodiode PD1 and the second photodiode PD2 are formed in thesemiconductor substrate 22. The transmission transistors Tr12 and Tr13of the first photodiode PD1 and the second photodiode PD2 are formed onthe front surface of the semiconductor substrate 22. The organicphotoelectric conversion unit 39 and the thin film transistor Tr14 areformed on the rear surface of the semiconductor substrate 22 with theinsulating layer 34 interposed therebetween.

In this embodiment, as described above, the solid-state imaging deviceincludes the organic photoelectric conversion unit 39 executing thephotoelectric conversion to the green-wavelength light, the firstphotodiode PD1 executing the photoelectric conversion to theblue-wavelength light, and the second photodiode PD2 executing thephotoelectric conversion to the red-wavelength light.

FIG. 46 is a diagram illustrating the vertical cross-sectionconfiguration of the pixel section (imaging region). In this embodiment,conductive plugs, which commonly connect the drain regions D of the thinfilm transistors. Tr14 of the pixels arranged in a vertical line to eachother and are connected to the drain regions D, are shared by oneconductive plug 101. Therefore, each thin film and the drain region D ofthe transistor Tr14 are connected to a common wiring 99 in each of thepixels arranged in each vertical line. Each common wiring 99 isconnected to one conductive plug 101.

Conductive plugs, which commonly connect the gate electrodes 86 of thethin film transistors Tr14 of the pixels arranged in a vertical line toeach other and are connected to gate electrodes 86, are commonly used byone conductive plug 83 (see FIG. 43 ).

As shown in a circuit diagram of FIG. 47 , the upper electrode 37 on theorganic photoelectric conversion unit 39 of each pixel is connected tothe drain D of the thin film transistor Tr14. The drains of the thinfilm transistors Tr14 of each row vertically arranged are commonlyconnected to each other and connected to the conductive plug 101. On theother hand, the gates of the thin film transistors Tr14 of each rowarranged vertically are commonly connected to each other and areconnected to the conductive plug 83.

It is desirable that the common wiring 99 is formed so as to avoid thelight-sensing opening of each pixel. However, the common wiring 99 maybe formed so as to cross the light-sensing opening when the transparentconductive layer is formed. The common wiring 99 may be formed in theinsulating layer 34. The conductive plugs 101 and 83 are likely todeteriorate a noise or reduce the size of a pixel, when the conductiveplugs 101 and 83 are disposed in the pixel. Therefore, the conductiveplugs 101 and 83 are formed on the side of the peripheral circuit.

Since the other configuration is the same as that of the sixthembodiment, the same reference numerals are given to the units of FIG.46 corresponding to the units in FIG. 35 and the repeated description isomitted.

In the solid-state imaging device 98 according to the seventhembodiment, since it is not necessary to form one conductive plug 101formed through the semiconductor substrate 22 in each pixel, it ispossible to reduce the number of conducive plugs. Therefore, the area ofthe light-sensing passage of the photoelectric conversion unit can bebroadened. Since the number of conductive plugs can be reduced, it ispossible to suppress a noise in the pixel of blue (B) or red (R) due tothe conductive plug.

In the seventh embodiment, as in the above-described embodiments, theorganic photoelectric conversion unit 39 may be close to the twophotodiodes PD1 and PD2. Even when the dependence on the F numbers ofthe colors is suppressed and the F numbers are changed, it is possibleto suppress the variation in the sensitivity between the colors withoutthe variation in the spectral balance of each color. Since the negativevoltage VL (<0 V) is applied to the lower electrode 38 at the time ofaccumulating the charges, the interface with the silicon insulatinglayer 34 becomes the hole accumulation state. When the insulating layer34 has the negative fixed charges, the hole accumulation state isfurther enhanced and it is possible to suppress the dark current.

9. Eighth Embodiment Exemplary Configuration of Solid-State ImagingDevice

In FIGS. 48 and 49 (schematic diagrams), a solid-state imaging deviceaccording to an eighth embodiment of the invention is shown. Thesolid-state imaging device according to this embodiment is aback-illuminated CMOS solid-state imaging device. In a solid-stateimaging device 103 according to the eighth embodiment, as in theabove-described embodiments, the organic photoelectric conversion unit39 for the first color, the first photodiode PD1 for the second color,and the second photodiode PD2 for the third color are laminated in thedepth direction in the same pixel.

In this embodiment, as described above, the solid-state imaging deviceincludes the organic photoelectric conversion unit 39 executing thephotoelectric conversion to the green-wavelength light, the firstphotodiode PD1 executing the photoelectric conversion to theblue-wavelength light, and the second photodiode PD2 executing thephotoelectric conversion to the red-wavelength light.

In this embodiment, as shown in FIGS. 48 and 49 , the pixels arearranged in the matrix form, and the photodiodes PD [PD1 and PD2] of twopixels 20 [201 and 202] are arranged diagonal to each other and shareone floating diffusion unit (FD) 104. That is, in the solid-stateimaging device 103 shown in FIG. 49 (schematic sectional view), thefirst photodiode PD1 and the second photodiode PD2 are formed in thesame pixel 20 of the semiconductor substrate 22, and the organicphotoelectric conversion unit 39 is formed on the rear surface 23 of thesubstrate with the insulating layer 34 interposed therebetween. Theorganic photoelectric conversion unit 39 includes the organicphotoelectric conversion layer 36 and includes the upper electrode 37and the lower electrode 38 which interpose the organic photoelectricconversion layer 36.

On the side of the front surface 24 of the substrate, one floatingdiffusion unit (FD) 104 is formed between the photodiodes PD [PD1 andPD2] of the two pixels 201 and 202 arranged diagonal to each other. Agate electrode 105 of a transmission transistor Tr21 is formed betweenthe floating diffusion unit (FD) 104 and the n-type semiconductor region(charge accumulation layer) 29 of the first photodiode PD1 of one pixel201. A gate electrode 106 of the transmission transistor Tr22 is formedbetween the floating diffusion unit (FD) 104 and the n-typesemiconductor region (charge accumulation layer) 32 of the secondphotodiode PD2 of the other pixel 202.

Although not shown, in the organic photoelectric conversion unit. 39 ofeach pixel 20 [201 and 202], one floating diffusion unit (FD) is formedin each pixel. On the side of the front surface 24 of the substrate, themulti-layer wiring layer 58 having the wirings 57 of the plural layersis formed, and the supporting substrate 59 is attached to themulti-layer wiring layer 58. On the side of the rear surface 23 of thesubstrate, the unit corresponding to the on-chip lens in FIG. 1 isformed above the organic photoelectric conversion unit 39 with theplanarization layer 61. The same reference numeral is given and therepeated description is omitted.

An operation. (driving method) of the solid-state imaging device 103according to the eighth embodiment will be described. As in the firstembodiment, when light is incident from the rear surface 23 of thesubstrate 22 at the time of accumulating the charges, thegreen-wavelength light is subjected to photoelectric conversion in theorganic photoelectric conversion unit 39 and the signal charges(electrons) are generated and accumulated in the charge accumulationlayer (not shown). In the first photodiode PD1 the blue-wavelength lightis subjected to photoelectric conversion and the signal charges(electrons) are generated and accumulated in the n-type semiconductorregion 29. In the second photodiode PD2 the red-wavelength light issubjected to photoelectric conversion and the signal charges (electrons)are generated and accumulated in the n-type semiconductor region 32.

At the time of reading the charges, transmission pulses are applied tothe gate electrode 105 and 106 of the transmission transistors Tr21 andTr22 at different time. For example, when the transmission transistorTr21 is turned on, blue signal charges eB of the pixel 201 aretransmitted to one floating diffusion unit (FD) 104 via the transmissiontransistor Tr21, are converted into pixel signals, and are output. Next,when the transmission transistor Tr22 is turned on, red signal chargeseR of the pixel 202 are transmitted to the other floating diffusion unit(FD) 104 via the transmission transistor Tr22, are converted into pixelsignals, and are output.

Green signal charges in the organic photoelectric conversion unit. 39are transmitted to the floating diffusion unit (FD) disposed in eachpixel, are converted into pixel signals, and are output.

In the solid-state imaging device 103 according to the eighthembodiment, the photodiodes PD of two pixels adjacent to each othershare one floating diffusion unit (FD) 104. With such a configuration,even when the pixels become minute, the area of the photoelectricconversion unit can be broadened. Therefore, even when the pixels becomeminute, is possible to improve the sensitivity.

According to the eighth embodiment, as in the above-describedembodiments, the organic photoelectric conversion unit 39 is close tothe two photodiodes PD1 and PD2. Even when the dependence on the Fnumbers of the colors is suppressed and the F numbers are changed, it ispossible to suppress the variation in the sensitivity between the colorswithout the variation in the spectral balance of each color. Since thenegative voltage VL (<0 V) is applied to the lower electrode 38 at thetime of accumulating the charges, the interface with the siliconinsulating layer 34 becomes the hole accumulation state. When theinsulating layer 34 has the negative fixed charges, the holeaccumulation state is further enhanced and it is possible to suppressthe dark current.

In FIG. 49 , the transmission transistors connected to the photodiodesPD [PD1 and PD2] have the gate electrode in which the transmissionelectrode is formed in a planar form. However, the vertical typetransistor may be also possible in FIG. 48 .

FIG. 50 is a schematic diagram illustrating the configuration in whichthe transmission transistors of the photodiodes PD are configured as thevertical type transistors. In this embodiment, the first photodiode PD1and the second photodiode PD2 are formed in the same pixel 20 of thesemiconductor substrate 22. The organic photoelectric conversion unit 39is formed on the rear surface. 23 of the substrate with the insulatinglayer 34 interposed therebetween. The organic photoelectric conversionunit 39 includes the organic photoelectric conversion layer 36 andincludes the upper electrode 37 and the lower electrode 38 whichinterpose the organic photoelectric conversion layer 36.

The p-type semiconductor region 28 and the n-type semiconductor region29 serving as the hole accumulation layer and forming the firstphotodiode PD1 and the p-type semiconductor region 31 and the n-typesemiconductor region 32 forming the second photodiode PD2 are laminatedin parallel in the depth direction. On the front surface 24 of thesemiconductor substrate 22, one floating diffusion unit (FD) 104 isformed between the two pixels 201 and 202 arranged diagonal to eachother in FIG. 48 . Vertical type gate electrodes 112 and 113 forming thevertical transmission transistors Tr31 and Tr32 and buried in the depthdirection of the substrate 2 with the gate insulating layer 111interposed therebetween are formed with the photodiodes PD [PD1 and PD2]of each pixel interposed therebetween. The surface of the gate electrode113 of the n-type semiconductor region 29 of the first photodiode PD1 iscovered with a high-concentration p-type semiconductor region 115. Thesurface of the gate electrode 112 of the n-type semiconductor region 32of the second photodiode PD2 is covered with a high-concentration p-typesemiconductor region 114.

When the transmission transistor Tr31 is turned on at the time ofreading the charges, the blue signal charges eB accumulated in then-type semiconductor region 29 of the first photodiode PD1 aretransmitted to one floating diffusion unit. (FD) 104 via the channelregion 116. Next, when the transmission transistor Tr32 is turned on,the red signal charges eR accumulated in the n-type semiconductor region32 of the second photodiode PD2 are transmitted to the other floatingdiffusion unit (FD) 104 via the channel region 117.

In this way, the area of the photoelectric conversion unit of the pixelcan be broadened in the vertical type transmission transistor, comparedto the planar type transistor. Accordingly, it is advantageous when thepixels become minute.

10. Ninth Embodiment Exemplary Configuration of Electronic Apparatus

The solid-state imaging device according to the above embodiments of theinvention is applicable to an electronic apparatuses such as a camerasystem such as a digital camera or a video camera, a cellular phonehaving an imaging function, or other apparatuses having an imagingfunction.

FIG. 52 is a diagram illustrating a camera as an example of anelectronic apparatus according to a tenth embodiment of the invention.The camera according to this embodiment is an exemplary video cameracapable of imaging a still image or a moving image. A camera 121according to this embodiment includes a solid-state imaging device 122,an optical system 123 guiding incident light to a light-sensing sensorof the solid-state imaging device 122, and a shutter device 124. Thecamera 121 includes a driving circuit 125 driving the solid-stateimaging device 122 and a signal processing circuit 126 processing anoutput signal of the solid-state imaging device 122.

One of the solid-state imaging devices according to the above-describedembodiments is applied to the solid-state imaging device 122. Theoptical system (optical lens) 123 images image light (incident light)from a subject on an imaging surface of the solid-state imaging device122. At this time, signal charges are accumulated in the solid-stateimaging device 122 for a certain period. The optical system 123 may bean optical lens including plural optical lenses. The shutter device 124controls light-emitting time and light-shielding time for thesolid-state imaging device 122. The driving circuit 125 supplies adriving signal to control a transmission operation of the solid-stateimaging device 122 and a shutter operation of the shutter device 124.Signal transmission of the solid-state imaging device 122 is executed bythe driving signal (timing-signal) supplied from the driving circuit125. The signal processing circuit 126 executes various signalprocesses. An image signal subjected to the signal processes is storedin a memory medium such as a memory device or is output to a monitor.

In the electronic apparatus according to the tenth embodiment, since theorganic photoelectric conversion unit is close to two photodiodes in thesolid-state imaging device, the dependence on the F numbers of red,green, and blue is suppressed. Therefore, even when the F-number ischanged, the spectral balance of each color is not varied and thevariation in the sensitivity between colors can be prevented. Since theinterface with the silicon insulating layer can be set to the hole,accumulation state in the photodiode, the occurrence of the dark currentis suppressed. Therefore, it is possible to supply an electronicapparatus with high resolution and high quality.

It should be understood by those skilled in the art that variousmodifications, combinations, sub-combinations and alterations may occurdepending on design requirements and other factors insofar as they arewithin the scope of the appended claims or the equivalents thereof.

What is claimed is:
 1. A solid state imaging device comprising: asubstrate having oppositely facing first and second surfaces; aphotoelectric conversion unit layer having a light incident side facingaway from the substrate; a first photoelectric conversion unit and asecond photoelectric conversion unit within the substrate; and a thirdphotoelectric conversion unit within the photoelectric conversion unitlayer.
 2. The solid state imaging device according to claim 1 whereinthe first and second photoelectric conversion units overlay each other.3. The solid state imaging device according to claim 1 wherein the firstand second photoelectric conversion units comprise inorganicphotoelectric conversion material and the third photoelectric conversionunit comprises an organic photoelectric conversion material.
 4. Thesolid state imaging device according to claim 1 wherein (1) the firstsubstrate surface faces the light incident side and the second substratesurface faces away from the incident light surface, (2) the firstphotoelectric conversion unit is between the first substrate surface andthe second photoelectric conversion unit, and (3) the secondphotoelectric conversion unit is between the first photoelectricconversion unit and the second substrate surface.
 5. The solid stateimaging device according to claim 4 wherein the first photoelectricconversion unit is particularly sensitive to blue light, the secondphotoelectric conversion unit is particularly sensitive to red light andthe third photoelectric conversion unit is particularly sensitive togreen light.
 6. The solid state imaging device according to claim 1, thethird photoelectric conversion unit further comprises: a photoelectricconversion material layer; an upper electrode on a surface of thephotoelectric conversion material layer facing the light incidentsurface; and a lower electrode on a surface of the photoelectricconversion material layer facing the substrate, wherein, a signal chargein the third photoelectric conversion unit is transferred therefrom viathe lower electrode.
 7. The solid state imaging device according toclaim 6 wherein an insulating layer having a fixed negative voltage isbetween the photoelectric conversion unit layer and the substrate. 8.The solid state imaging device according to claim 7 wherein the lowerelectrode is provided with negative voltage and the upper electrode isprovided with positive voltage for driving the third photoelectricconversion unit.
 9. The solid state imaging device according to claim 6,further comprising a first insulating layer on each edge of the thirdphotoelectric conversion material layer.
 10. The solid state imagingdevice according to claim 1, further comprising a charge accumulationlayer within the substrate adjacent the second substrate surface. 11.The solid state imaging device according to claim 6, further comprisinga charge accumulation layer within the substrate adjacent the secondsubstrate surface.
 12. The solid state imaging device according to claim1, wherein an insulating layer having a fixed negative voltage isbetween the photoelectric conversion unit layer and the substrate. 13.The solid state imaging device according to claim 12 wherein theinsulating layer is made of HfO₂.
 14. The solid state imaging deviceaccording to claim 1 further comprising a thin film transistor withinthe photoelectric conversion unit layer, the thin film transistorconfigured to read a signal charge of the third photoelectric conversionunit.
 15. solid state imaging device comprising a plurality of pixelsarranged in a matrix having rows and columns, each pixel comprising: atleast a portion of a substrate having oppositely facing first and secondsubstrate surfaces; a photoelectric conversion unit layer having a lightincident side facing away from the substrate; a first photoelectricconversion unit and a second photoelectric conversion unit within the atleast a portion of a substrate; and a third photoelectric conversionunit within the photoelectric conversion unit layer.
 16. The solid stateimaging device according to claim 15, wherein each pixel furthercomprises a thin film transistor within the photoelectric conversionunit layer, the thin film transistor configured to read a signal chargeof the third photoelectric conversion unit.
 17. The solid state imagingdevice according to claim 16, wherein drain regions of the thin filmtransistors arranged along a common vertical line are commonly connectedvia a common wire.
 18. The solid state imaging device according to claim15, wherein the first and second photoelectric conversion units of apair of pixels diagonally adjacent to each other relative to the rowsand columns share a floating diffusion unit.
 19. A solid state imagingdevice comprising: a substrate having oppositely facing first and secondsurfaces; a photoelectric conversion unit layer having a light incidentside facing away from the substrate; a first photoelectric conversionunit and a second photoelectric conversion unit within the substrate; athird photoelectric conversion unit within the photoelectric conversionunit layer; and a multi-wiring layer outside of the substrate andlocated in a layer carried on the second substrate surface. 20-22.(canceled)